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용융탄산염형 연료전지 분리판 재료의 부식거동

  • 이충곤
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 1998.05a
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    • pp.21-21
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    • 1998
  • 새로운 에너지원으로 각광받고 있는 연료전지는 우주선 동력윈으로서의 이용이래, 보다 실용적인 발전 시스템을 목적으로 많은 연구개발이 시도되고 있다. 이러한 연료전지는 사용하는 전해질의 특성으로 인하여 저온형($<300^{\circ}C$) 과 고온형($500^{\circ}C<$)으로 구분된 수 있는데, 저온형 연료전지의 경우는 전극반응 특성상 귀금속 촉매가 필요한 데 비해, 고온형 연료전지는 이러한 귀금속 촉매가 필요없다는 점등에서 다양한 장점을 가지게 된다. 즉, 저온형에 비해 다양한 연료가 가능하고, 대형화에 유리함며, 고온 페열을 이용할 수 있는 점 등을 들 수 있다. 용융탄산염형 연료전지(MFCFC)는 이러한 고온형 연료진지의 장점을 배경으로 현재 대규모의 개발이 진행되고 있다. 그러나 여기에 주로 사용되는 Li-K, Li-Na와 같은 용융탄신엽은 고부식성 전해질로서 대부분의 금속이 산화물을 형성하는 것으로 알려져 있다. MCFC의 분리판은 셀간을 전기적으로 이어주는 역할, 가스의 유로제공 및 가스 Sealing의 역할을 담당하는 부분으로서, 분리판의 부식은 이러한 특성의 저하 및 전해질의 소모를 유발시켜 MCFC의 내구성에 커다란 영향 을 미치는 요인으로 생각되고 있다. 이러한 배경으로부터 Uchida 그룹은 MCFC의 분라판 재료 의 부식거동을 계동적으로 검토하였다. 먼저 Fe에 Ni 과 Cr을 첨가한 재료를 산화성가스 분위기하에서 $(Li+K)CO_3$에 대하여 검토한 결과, Ni과 Cr 둘다 20wt%이상 첨가시, 내식성융 가지는 결 과를 보고하였다2) 이 경우 보호피막으로서 NiO 와 $LiCrO_2$가 작용하는데, $LiCrO_2$가 용융탄산염 중에서 보다 안정한 것으로 부터, Cr의 첨가가 내식성에 기여하는 것으로 판단하였다. 다음 단계 로서 Fe/Cr재료에 용-융탄산염 중에서 안정한 산화물을 형성하는 Al의 첨가효과를 검토하였다. Al의 첨가는 더욱 내식성을 향상시키는 것이 발견되었고, 약 4wt%의 첨가로 충분한 내식성을 가지 는 것을 보고 하였다. 그러나 이러한 안정한 산화물에 의한 내식성 향상은 전기진도도의 희생을 바탕으로 한 것으로서, 다읍 단계로서 Ti산화물의 반도체적인 특성을 이용하고자 제 4의 원소로서 Ti첨가를 시도하였다. 그러나 Fe/Cr/AVTi재료가 뛰어난 내식성을 가지는 것은 관찰되었으나, 전도도 향상에는 기여하지 못하는 것이 보고되었다. 현재 MCFC는 실용화를 위한 고성능화의 하나로서 가압하에서의 운전을 시도하고 있다. 이 러한 가압하에서의 운전은 기전력의 향상 및 전극반응의 촉진 등으로 출력의 향상을 가져오나. 현재 문제로 되고 있는 Cathode극인 NiO의 용해/석출 현상을 가속화하는 결과를 초래해, 이에대 한 대책으로서 Li-K보다 NiO의 용해가 적은 Li-Na탄산염으로의 전환이 진행되고 있다. 이러한 배경으로부터 Uchida그룹에서 개발한 FeiCr/AVTi재료와 현재 분리판 재료로 사용증인 SUS 310, S SUS 316재료에 대해. 산화성 분위기의 5기압까지의 가압하에서, Li-K, Li-Na탄산염에 대하여 부 식거동을 검토한 결과, 가압하에서 내식성이 향상되는 것이 발견되었다. 이유로서는 가압하에서 용융탄산엽의 증가된 산화력으로 보다 치밀한 내식성 산화물 피막이 형성되기 때문으로 생각되고 있다. 또한 Li-K, Li-Na탄산염에서의 부식의 정도에는 차이가 거의 없었으나, SUS 316의 경우 탄산염에 젖은 부분에서 내식성 피막이 형성되지 않는 이상부식현상이 관찰되었다. 재료간의 내식성 정도에서는 Fe/Cr/Al/Ti이 가장 내식성이 뛰어났으며, SUS 310 또한 뛰어난 내식성을 보였다.

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Decontamination of simulated radioactive metal waste by modified electrolytic Process with neutral salt electrolytes (개선된 중성염 진해공정을 이용한 모의 방사성 금속폐기물의 제염)

  • Lee, Ji-Hoon;Yuk, Wan-Yi;Yang, Ho-Yeon;Ha, Jong-Hyun
    • Journal of Radiation Protection and Research
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    • v.27 no.2
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    • pp.95-100
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    • 2002
  • Conventional and modified electrolytic decontamination experiment were performed in the 1.7 M solution of sodium sulfate and sodium nitrate tot decontamination of carbon steel as the simulated metal wastes which have been produced in large amounts from nuclear power plants. Anode ant cathode were used as inconel and titanium respective. The reaction time and temperature were 1 hr and $25^{\circ}C$ The analyses were performed of the characteristics such as weight loss arid thickness change of metal waste. suspended solid in electrolyte and SEM observation. In modified electrolyte decontamination system with increased current density ranged from 0.1 to $0.6A/cm^2$, the metal waste showed thickness changes of $0.48{\pm}0.005$ to $67.7{\pm}0.02{\mu}m$ in 1.7 M sodium sulfate and those of $0.06{\pm}0.005$ to $17.7{\pm}0.05{\mu}m$ in sodium nitrate. Metal waste in modified electrolyte decontamination system showed the thickness change of $9.8{\pm}0.01{\mu}m$ while it reacted up to $3.7{\pm}0.03{\mu}m$ in conventional system with $0.3 A/cm^2$ of current density and 1.7 M sodium sulfate. Decontamination efficiencies of modified electrolytic process ate much hither than that of conventional electrolytic process when both are applied to metal waste.

Electrolytic Reduction of 1 kg-UO2 in Li2O-LiCl Molten Salt using Porous Anode Shroud (Li2O-LiCl 용융염에서의 다공성 양극 슈라우드를 이용한1kg 우라늄산화물의 전해환원)

  • Choi, Eun-Young;Lee, Jeong;Jeon, Min Ku;Lee, Sang-Kwon;Kim, Sung-Wook;Jeon, Sang-Chae;Lee, Ju Ho;Hur, Jin-Mok
    • Journal of the Korean Electrochemical Society
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    • v.18 no.3
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    • pp.121-129
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    • 2015
  • The platinum anode for the electrolytic reduction process is generally surrounded by a nonporous ceramic shroud with an open bottom to offer a path for $O_2$ gas produced on the anode surface and prevent the corrosion of the electrolytic reducer. However, the $O^{2-}$ ions generated from the cathode are transported only in a limited fashion through the open bottom of the anode shroud because the nonporous shroud hinders the transport of the $O^{2-}$ ions to the anode surface, which leads to a decrease in the current density and an increase in the operation time of the process. In the present study, we demonstrate the electrolytic reduction of 1 kg-uranium oxide ($UO_2$) using the porous shroud to investigate its long-term stability. The $UO_2$ with the size of 1~4mm and the density of $10.30{\sim}10.41g/cm^3$ was used for the cathode. The platinum and 5-layer STS mesh were used for the anode and its shroud, respectively. After the termination of the electrolytic reduction run in 1.5 wt.% $Li_2O-LiCl$ molten salt, it was revealed that the U metal was successfully converted from the $UO_2$ and the anode and its shroud were used without any significant damage.

A study on the electrochemical reduction of carbon dioxide (전기화학환원에 의한 이산화탄소의 수소화 반응연구)

  • Sim, Kyu-Sung;Kim, Jong-Won;Kim, Yeon-Soon;Myeong, Kwang-Sik
    • Journal of Hydrogen and New Energy
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    • v.9 no.1
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    • pp.8-15
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    • 1998
  • The catalytic hydrogenation of carbon dioxide has been studied for the fixation of carbon dioxide to mitigate global warming problems, but it needed hydrogen, which the price is still high. Recently, the electrochemical reduction of carbon dioxide has been drawn attractions because carbon dioxide could be converted to the valuable chemicals such as methane, ethane and alcohols electrochemically in the electrolyte solution using a catalytic electrode. This system is simple because the water electrolysis and hydrogenation take place at the same time using the surplus electricity at midnight. In this work, a continuous electrochemical reduction system was fabricated, which was composed of the reduction electrode (copper or perovskite type, $2{\times}2cm^2$), reference electrode(platinum, $2{\times}6cm^2$), standard electrode(Ag/AgCl), and potassium bicarbonate electrolyte solution saturated with carbon dioxide. The quality and quantity of the products and reduction current were analyzed, according to the electrolyte concentration and electrode type.

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Electrochemical Template Synthesis of Conducting Polymer Microstructures at Addressed Positions (템플레이트의 국소 위치에 형성된 전도성 고분자 미세구조물의 전기화학 합성)

  • Lee Seung Hyoun;Suh Su-Jeong;Yun Geum-Hee;Son Yongkeun
    • Journal of the Korean Electrochemical Society
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    • v.7 no.2
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    • pp.100-107
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    • 2004
  • The nano or micro sized structures of conducting polymer had been prepared by synthesizing the desired polymer within the pores of template of nano or micro porous membrane filter. In this study, we had tried to fabricate conducting polymer microstructures on an electrode by using electrochemical deposition adopting template synthesis. Our attention was focused on two different things, attaching template on the electrode and fabricating microstructures only at limited areas of the electrode. A conducting polymer, PEDiTT (poly 3,4-ethylenedithi-athiophene) solution was blended with PVA(polyvinyl alcohol) solution and used as an conducting adhesive. After attaching template membrane, the electrode were immersed in 0.5M pyrrole in 0.1M KCI solution, and electrochemical polymerization was performed. The growth process of the microstructures studied by SEM. The electrochemical fabrication of conducting polymer was performed by using two-electrode system. A large working electrode and a micro scale disc electrode were used for the confined area synthesis. Polymerization potential was 4V in an electrolytic solution made of KCI in deionized water. The optimum polymerization conditions were, i.e. (4V/100sec) for $250{\mu}m$ electrode and (6V/30 sec) for $10{\mu}m$ electrode.

Optimization of anode and electrolyte microstructure for Solid Oxide Fuel Cells (고체산화물 연료전지 연료극 및 전해질 미세구조 최적화)

  • Noh, Jong Hyeok;Myung, Jae-ha
    • Korean Chemical Engineering Research
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    • v.57 no.4
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    • pp.525-530
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    • 2019
  • The performance and stability of solid oxide fuel cells (SOFCs) depend on the microstructure of the electrode and electrolyte. In anode, porosity and pore distribution affect the active site and fuel gas transfer. In an electrolyte, density and thickness determine the ohmic resistance. To optimizing these conditions, using costly method cannot be a suitable research plan for aiming at commercialization. To solve these drawbacks, we made high performance unit cells with low cost and highly efficient ceramic processes. We selected the NiO-YSZ cermet that is a commercial anode material and used facile methods like die pressing and dip coating process. The porosity of anode was controlled by the amount of carbon black (CB) pore former from 10 wt% to 20 wt% and final sintering temperature from $1350^{\circ}C$ to $1450^{\circ}C$. To achieve a dense thin film electrolyte, the thickness and microstructure of electrolyte were controlled by changing the YSZ loading (vol%) of the slurry from 1 vol% to 5 vol. From results, we achieved the 40% porosity that is well known as an optimum value in Ni-YSZ anode, by adding 15wt% of CB and sintering at $1350^{\circ}C$. YSZ electrolyte thickness was controllable from $2{\mu}m$ to $28{\mu}m$ and dense microstructure is formed at 3vol% of YSZ loading via dip coating process. Finally, a unit cell composed of Ni-YSZ anode with 40% porosity, YSZ electrolyte with a $22{\mu}m$ thickness and LSM-YSZ cathode had a maximum power density of $1.426Wcm^{-2}$ at $800^{\circ}C$.

Effect of AlF3 on Zr Electrorefining Process in Chloride-Fluoride Mixed Salts for the Treatment of Cladding Hull Wastes (폐 피복관 처리를 위한 염소계-불소계 혼합용융염 내 지르코늄 전해정련공정에서 삼불화알루미늄의 효과 연구)

  • Lee, Chang Hwa;Kang, Deok Yoon;Lee, Sung-Jai;Lee, Jong-Hyeon
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.17 no.2
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    • pp.127-137
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    • 2019
  • Zr electrorefining is demonstrated herein using Zirlo tubes in a chloride-fluoride mixed molten salt in the presence of $AlF_3$. Cyclic voltammetry reveals a monotonic shift in the onset of metal reduction kinetics towards positive potential and an increase in intensity of the additional peaks associated with Zr-Al alloy formation with increasing $AlF_3$ concentration. Unlike the galvanostatic deposition mode, a radial plate-type Zr growth is evident at the top surface of the salt during Zr electrorefining at a constant potential of -1.2 V. The diameter of the plate-type Zr deposit gradually increases with increasing $AlF_3$ concentration. Scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDX) and X-ray photoelectron spectroscopy (XPS) analyses for the plate-type Zr deposit show that trace amount of Al is incorporated as Zr-Al alloys with different chemical compositions between the top and bottom surface of the deposit. Addition of $AlF_3$ is effective in lowering the residual salt content in the deposit and in improving the current efficiency for Zr recovery.

Investigation of a Thermal Stress for the Unit Cell of a Solid Oxide Fuel Cell (고체산화물 연료전지 단위셀의 열응력에 관한 연구)

  • Kim, Young-Jin;Park, Sang-Kyun;Roh, Gill-Tae;Kim, Mann-Eung
    • Journal of Advanced Marine Engineering and Technology
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    • v.35 no.4
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    • pp.414-420
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    • 2011
  • Thermal stress analysis of a planar anode-supported SOFC considering electrochemical reactions has been performed under operating conditions where average current density varies from 0 to 2000 $A/m^2$. For the case of the 2000 $A/m^2$ operating condition, Structural stress analysis based on the temperature distributions obtained from the CFD analysis of the unit cell has also been done. From this one way Fluid-Structure Interaction(FSI) analysis, Maximum Von-Mises stress under negligible temperature gradient fields occurs when cell components are perfectly bonded. The maximum stress of the electrolyte, cathode and anode in a unit cell SOFC is 262.58MPa, 28.55MPa and 15.1MPa respectively. The maximum thermal stress is critically dependent on static friction coefficient.

Preparation of $Ce_{0.8}Sm_{0.2}O_{x}$ Electrolyte Thin Film for Solid Oxide Fuel Cells by Electrophoretic Deposition (전기영동법을 이용한 고체산화물 연료전지용 $Ce_{0.8}Sm_{0.2}O_{x}$ 전해질 박막 제조)

  • Kim, Dong-Gyu;Song, Min-Wu;Lee, Kyeong-Seop;Kim, Yoen-Su;Kim, Young-Soon;Shin, Hyung-Shik
    • Korean Chemical Engineering Research
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    • v.49 no.6
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    • pp.781-785
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    • 2011
  • In this work, a nano-sized samaria-doped ceria(SDC) was prepared by a urea-based hydrothermal method and characterized by XRD, FESEM and TEM. It was observed that the increase in synthesis time and temperature gave rise to crystallity and particles size. Moreover, the synthesised powders had a excellent ion-conductivity(0.1 S/cm at 600~$800^{\circ}C$) which is suitable for electrolyte of intermediate temperature-solid oxide fuel cell(IT-SOFC). Subsequently for use as electrolyte for anode-supported IT-SOFC, we tried to deposit the SDC powder on a porous NiO-SDC substrate by electrophoretic deposition(EPD) method. From the FESEM observation, a compact

Research and Development Trend of Electrolyte Membrane Applicable to Water Electrolysis System (수전해 시스템에 적용 가능한 전해질막 연구 개발 동향)

  • Im, Kwang Seop;Son, Tae Yang;Kim, Kihyun;Kim, Jeong F.;Nam, Sang Yong
    • Applied Chemistry for Engineering
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    • v.30 no.4
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    • pp.389-398
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    • 2019
  • Hydrogen energy is not only a solution to climate change problems caused by the use of fossil fuels, but also as an alternative source for the industrial power generation and automotive fuel. Among hydrogen production methods, electrolysis of water is considered to be one of the most efficient and practical methods. Compared to that of the fossil fuel production method, the method of producing hydrogen directly from water has no emission of methane and carbon dioxide, which are regarded as global environmental pollutants. In this paper, the alkaline water electrolysis (AWE) and polymer electrolyte membrane water electrolysis (PEMWE), which are one of the hydrogen production methods, were discussed. Recent research trends of hydrocarbon electrolyte membranes and the crossover phenomenon of electrolyte membranes were also described.