• Title/Summary/Keyword: 고온 고분자 전해질막 연료전지

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A Study on Organic/Inorganic Composite Membrane for Low humidity and High Temperature Polymer Electrolyte Membrane Fuel Cells (저가습 고온 고분자 연료전지용 유-무기 복합막에 관한 연구)

  • Choi, Young-Woo;Kim, Mi-Nai;Lim, Sung-Dae;Park, Seok-Hee;Yoon, Young-Gi;Yang, Tae-Hyun;Kim, Chang-Soo;Nam, Ki-Sook
    • 한국신재생에너지학회:학술대회논문집
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    • 2010.06a
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    • pp.135.1-135.1
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    • 2010
  • 최근 고온에서 사용 가능한 PEMFC용 고분자전해질 막 개발에 대한 연구가 활발히 진행되고 있다. PEMFC가 고온에서 작동하게 되면 높은 성능과 많은 장점을 갖게 된다. PEMFC를 $100^{\circ}C$ 이상에서 운전하게 될 경우 백금 전극 반응을 향상시켜 고가의 백금 촉매 양을 줄일 수 있게 되고, 수소연료 속에 미량 포함된 CO에 의한 촉매표면 피독현상에 대한 내구성을 높일 수 있어 저 순도 수소연료 사용이 가능해 진다. 또한 가습장치와 수소 연료 개질장치의 부피를 줄일 수 있게 되어 전체적인 PEMFC 시스템이 단순화 된다. 현재 연료전지용 고분자 전해질막으로 DuPont사의 과-불소계 고분자 전해질막인 Nafion$^{(R)}$이 가장 널리 사용되고 있다. Nafion$^{(R)}$은 유연한 분자구조 안에 소수성이 강한 주사슬과 친수성을 나타내는 술폰산이 결합된 곁사슬이 존재하여 술폰화 곁사슬의 클러스터 둘레에는 친수성 영역이 형성이 되기때문에 소수/친수 상 분리가 잘되어 이온 클러스터 형성이 용이하지만 제조비용이 높은 단점을 갖고 있다. 특히, 전해질 막내에서 Bronsted base 역할을 하는 물에 의해 이온전도가 이루어지기 때문에 고온에서는 수분증발로 인해 성능이 급격히 감소된다. 따라서, 본 연구에서는 고온 저가습 조건에서 운전이 가능하고 Nafion이 갖는 문제점을 해결하고자, 내열특성이 뛰어나며 높은 수소이온 전도도 학보가 용이한 Sulfonated Poly(aryl ether)sulfone(SPAES) 고분자 전해질에, 고온에서도 수화성이 유지될 수 있도록 지르코니아를 황산화한 sulfated zirconia(s-$ZrO_2$)를 함침하여 복합 고분자전해질막을 제조하여 고온 저가습 조건에서의 수소이온 전도 특성에 관한 연구를 수행하였다. 개발된 막의 물리/화학적 특성은 water content(Wup%), 이온교환 용량(IEC, meq $g^{-1}$), 수소이온전도도(s $cm^{-1}$) 열 중량 분석(TGA), X선 회절분석(XRD) 등을 통하여 분석 및 관찰하였다. 내화학 및 열적 특성분석 결과, 황산화 반응공정으로 $ZrO_2$에 술폰산기가 안정적으로 결합하고 있음이 관찰되었으며, 본 연구에서 개발된 유 무기 복합막이 $250^{\circ}C$이상 열적안정성을 확보하고 있는 것으로 판단되었다. $100^{\circ}C$ 이하의 저온 영역에서, 일정 비율의 s-$ZrO_2$/SPAES막에서 이온교환용량(IEC)이 순수 SPAES 막보다 낮음에도 불구하고, water uptake가 증가함과 동시에 수소이온 전도도가 향상된 것을 관찰하였다. 또한, 고온에서는 수소이온이 자유롭게 이동할 수 있는 water channel을 형성하는 free water는 증발 하지만 s-$ZrO_2$와 SPAES의 술폰산기 사이에 강력하게 결합하고 있는 bound Water는 $100^{\circ}C$ 이상의 고온 영역에서도 존재하여, 비록 무가습 조건에서도 일정 비율의 s-$ZrO_2$/SPAES50 전해질 막의 경우, 높은 전도도를 나타냄을 관찰할 수 있었다. 따라서 본 연구를 통해 저가습 고온 적용을 목적으로 개발된 s-$ZrO_2$/SPAES50막은 우수한 내열 특성을 나타냄과 동시에 저가습 고온 영역($120^{\circ}C$, $50RH{\downarrow}$)에서 높은 수소이온 전도도를 유지하여, 고온 저가습 연료전지 운전에 적합할 것으로 사료된다.

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Study on PEM-Fuel-Cell Humidification System Consisting of Membrane Humidifier and Exhaust Air Recirculation Units (막가습기와 공기극 재순환을 사용한 고분자 전해질 연료전지의 가습특성 해석)

  • Byun, Su-Young;Kim, Beom-Jun;Kim, Min-Soo
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.35 no.4
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    • pp.337-344
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    • 2011
  • The humidification of reactant gases is crucial for efficiently operating PEM (polymer electrolyte membrane) fuel cell systems and for improving the durability of these systems. The recycle of the energy and water vapor of exhaust gas improves the system performance especially in the case of automotive application. The available humidification methods are steam injection, nozzle spray, humidification by enthalpy wheel, membrane humidifier, etc. However, these methods do not satisfy certain requirements such as compact design, efficient operation and control. In this study, a hybrid humidification system consisting of a membrane humidifier and exhaust-air recirculation units was developed and the humidification performance of this hybrid humidifier was analyzed. Finally, a new practical method for optimal design of PEM-fuel-cell humidification system is proposed.

Synthesis and Property of Hydrophilic-Hydrophobic Random Multiblock Poly(ether sulfone)s as Polyelectrolytes for Fuel Cell Application (연료 전지용 소수성/친수성 랜덤 멀티블럭 공중합체의 합성과 특성)

  • Choi, Kyu-Buem;Kim, Sang-Un;Kim, Young-Jun;Hong, Young-Taik
    • 한국신재생에너지학회:학술대회논문집
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    • 2009.11a
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    • pp.197-198
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    • 2009
  • 고분자 전해질막으로 사용할 수 있는 소수성/친수성 랜덤 멀티블럭 공중합체를 합성하였다. 공중합체는 수산화기를 각 말단에 가지고 있는 소수성 올리고머, 친수성 올리고머 및 반응성이 좋은 커플링 단량체로 친핵성 치환 반응을 활용하여 합성 하였다. 높은 반응성의 커플링 단량체의 존재로 비교적 낮은 온도에서 합성이 됨으로서 고온에서의 에테르-에테르 교환반응에 의한 랜덤화를 억제할 수 있었으며, 높은 중합도의 공중합체를 합성 할 수 있었다. 각 수산화기로 같은 말단으로 조정된 올리고머는 투입 비율의 조정으로 쉽게 이온교환용량을 조정할 수 있었다. 솔루션 캐스팅 방법으로 강도를 가지고 잘 휘어지며 투명한 전해질막을 제조할 수 있었다. 전해질막은 이온전도도, 물흡수율, 부피 변화율, 연료 투과성 등의 측정이 되었다.

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Effect of operating conditions on carbon corrosion in High temperature polymer electrolyte membrane fuel cells (HT-PEMFCs) (고온형 고분자 전해질막 연료전지(HT-PEMFC) 구동환경에 따른 탄소 담지체 부식 평가)

  • Lee, Jinhee;Kim, Hansung
    • 한국신재생에너지학회:학술대회논문집
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    • 2011.11a
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    • pp.89.1-89.1
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    • 2011
  • The influence of potential and humidity on the electrochemical carbon corrosion in high temperature polymer electrolyte membrane fuel cells(HT-PEMFCs) is investigated by measuring $CO_2$ emission at different potentials for 30 min using on-line mass spectrometry. These results are compared with low tempterature polymer electrolyte membrane fuel cells(LT-PEMFCs) operated at lower temperature and higher humidity condition. Although the HT-PEMFC is operated at non humidified condition, the emitted $CO_2$ in the condition of HT-PEMFC is more than LT-PEMFC at the same potential in carbon corrosion test. Thus, carbon corrosion shows a stronger positive correlation with the cell temperature. In addition, the presence of a little amount of water activate electrochemical carbon corrosion considerably in HT-PEMFC. With increased carbon corrosion, changes in fuel cell electrochemical characteristics become more noticeable and thereby indicate that such corrosion considerably affects fuel cell durability.

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Current Patents and Papers Research Trend of Fuel Cell Membrane (특허 및 논문 게재 분석을 통한 연료전지용 전해질막의 연구동향)

  • Woo, Chang Hwa
    • Membrane Journal
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    • v.26 no.6
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    • pp.407-420
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    • 2016
  • The fuel cell technology as a green energy source has been actively studied to solve energy shortages and pollution problems. The generating efficiency of fuel cell is high because the electricity is directly produced by using hydrogen and oxygen and the additional power generator is not needed. The key technology is the manufacturing process of polymer electrolyte membranes for polymer electrolyte membrane fuel cell (PEMFC) system. The Nafion, perfluoro-based polymeric membrane is mainly used as a polymer electrolyte membrane. However, the Nafion is expensive and rapidly decreases the performance of Nafion at high temperature. So, many researchers are lively studying new alternative electrolyte membranes. In this review, through the technology competitiveness evaluation of patents and papers, the frequencies of presentation are filed by country, institution and company. In addition, polymer electrolyte membrane fuel cell, direct methanol fuel cell and alkaline fuel cell are also filed.

Development of PolymerElectrolytes Based on Ionic Liquids forHigh Temperature/Low Humidity PEFC Applications (고온/저가습 고분자전해질 연료전지를 위한 이온성 액체 기반 고분자 전해질막 개발)

  • Sekhon, Satpal Singh;Park, Jin-Soo;Cho, Eun-Kyung;Park, Gu-Gon;Kim, Chang-Soo;Lee, Won-Yong
    • 한국신재생에너지학회:학술대회논문집
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    • 2008.10a
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    • pp.40-43
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    • 2008
  • High temperature polymer electrolyte membranes incorporating ionic liquids (ILs) in different polymers such as commercial fluorinated polymers, sulfonated polymers and recasted nafion have been developed. ILs based on imidazolium cation and different anions possess high ionic conductivity and good thermal stability and have been used in the present study. The membranes containing IL show conductivity ${\sim}10^{-2}S\;cm^{-1}$ above $100^{\circ}C$ under anhydrous conditions and are thermally stable up to $250-300^{\circ}C$. IL acts as a conducting medium in these electrolytes and plays the same role as played by water in fully hydrated nafion membranes. Due to high conductivity and good thermal stability, these membranes are promising materials for PEFCs at higher temperatures under anhydrous conditions.

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Determination of Optimum Binder Content in the Catalyst Layer with Different GDL for Anode of HT-PEMFC (고온 고분자 전해질막 연료전지 수소극 전극에서 서로 다른 가스 확산층에 따른 최적 바인더 함량 결정)

  • CHUN, HYUNSOO;KIM, DO-HYUNG;JUNG, HYEON-SEUNG;PAK, CHANHO
    • Transactions of the Korean hydrogen and new energy society
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    • v.33 no.1
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    • pp.38-46
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    • 2022
  • Two different gas diffusion layers having noticeable differences in micro-porous layer's (MPL's) crack were studied as a substrate for the gas diffusion electrode (GDE) with different binder/carbon (B/C) ratios in high-temperature polymer electrolyte fuel cell (Ht-PEMFC). As a result, the performance defined as the voltage at 0.2 A/cm2 and maximum power density from the single cells using GDEs from H23 C2 and SGL38 BC with different B/C ratios were compared. GDEs from H23 C2 showed a proportional increase of the voltage with the binder content on the other hand GDEs from SGL38 BC displayed a proportional decline of the voltage to the binder content. It was revealed that MPL crack influences the structure of catalyst layer in GDEs as well as affects the RCathode which is in close connection with the Ht-PEMFC performance.

Characterization of Nafion/Poly(ether(amino sulfone)) Acid-base Blend Polymer Electrolyte Membranes for Direct Dimethyl Ether Fuel Cell (Nafion/poly(ether(amino sulfone)) 산-염기 블렌드 전해질막을 이용한 디메틸 에테르 직접연료전지 특성연구)

  • Park Sun-Mi;Choi Won-Choon;Nam Seung-Eun;Lee Kew-Ho;Oh Se-Young;Lee Chang-Jin;Kang Yong-Ku
    • Journal of the Korean Electrochemical Society
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    • v.9 no.2
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    • pp.89-94
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    • 2006
  • Nafion/poly(ether(amino sulfone)) acid-base blend polymer electrolyte membranes were prepared and their proton conductivity and dimethyl ether permeability were investigated. Characteristics of direct dimethyl ether fuel cell (DDMEFC) performance using prepared blend membrane were studied. The increase of amine groups in the base polymer in composite membranes resulted in the decrease in dimethyl ether permeability. The proton conductivity of the blend membranes gradually increased as increasing temperature. The conductivity of Nafion/PEAS-0.6 (85:15) blend membranes was measured to be $1.42\times10^{-2}S/cm\;at\;120^{\circ}C$ which was higher than that of the recast Nafion. The performance of direct dimethyl ether fuel cell (DDMEFC) using the Nafion/PEAS blend membranes was higher than that using $Nafion^(R)115$ membrane. Enhanced performance of direct dimethyl ether fuel cells using Nafion/PEAS blend membrane was explained by reducing dimethyl ether (DME) crossover through the electrolyte membrane and maintenance of the proton conductivity at high temperature.

Synthesis and Characterization of Phosphoric Acid-doped Poly (2,5-benzimidazole) Membrane for High Temperature Polymer Electrolyte Membrane Fuel Cells (고온 고분자 연료전지용 인산 도핑 폴리(2,5-벤지이미다졸) 막의 제조 및 특성)

  • Nguyen, Thi Xuan Hien;Mishra, Ananta Kumar;Choi, Ji-Sun;Kim, Nam-Hoon;Lee, Joong-Hee
    • Transactions of the Korean hydrogen and new energy society
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    • v.23 no.1
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    • pp.26-33
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    • 2012
  • Phosphoric acid-doped poly (2,5-benzimidazole) (DABPBI) was prepared by condensation polymerization of 3,4-diaminobenzoic acid for high temperature proton electrolyte membrane fuel cells. The membranes were casted directly using a hot-press unit and characterized by fourier transform infrared spectroscopy, thermogravimetric analysis, conductivity measurement, scanning electron microscopy and tensile test. The proton conductivities of DABPBI are observed to be 0.062 and 0.018 $S{\cdot}cm^{-1}$ under 30 and 1% relative humidity, respectively at a temperature of $120^{\circ}C$ which is appreciably higher than that of Nafion 115 under similar conditions. The DABPBI membrane has demonstrated excellent thermo- mechanical properties and proton conductivity suggesting its suitability as a high temperature membrane.

Anhydrous Crosslinked Polymer Electrolyte Membranes Based On ABA Triblock Copolymer (ABA 트리블록 공중합체를 이용한 무가습 가교형 고분자 전해질막)

  • Kim, Jong-Hak;Koh, Jong-Kwan;Lee, Do-Kyoung;Roh, Dong-Kyu;ShuI, Yong-Gun
    • Membrane Journal
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    • v.19 no.3
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    • pp.228-236
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    • 2009
  • ABA type triblock copolymer of poly(hydroxyl ethyl acrylate )-b-polystyrene-b-poly(hydroxyl ethyl acrylate), i.e. PHEA-b-PS-b-PHEA, was synthesized throughatom transfer radical polymerization (ATRP). This block copolymer was thermally crosslinked with 4,5-imidazole dicarboxylic acid (IDA) via the esterification between the -OH groups of PHEA in block copolymer and the -COOH groups of IDA. Upon doping with ${H_3}{PO_4}$ to form imidazole-${H_3}{PO_4}$ complexes, the proton conductivity of membranes continuously increased with increasing ${H_3}{PO_4}$ content. The PHEA-b-PS-b-PHEA/IDA/${H_3}{PO_4}$ polymer membrane with [HEA]:[IDA]:[${H_3}{PO_4}$]=3:4:4 exhibited a maximum proton conductivity of 0.01 S/cm at $100^{\circ}C$ under anhydrous conditions. Thermal gravimetric analysis (TGA) shows that the PHEA-b-PS-b-PHEA/IDA/${H_3}{PO_4}$ complex membranes were thermally stable up to $350^{\circ}C$, indicating their applicability in fuel cells.