• Korean Membrane Journal
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• 제9권1호
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• pp.43-51
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• 2007

This paper describes the preparation and characterization of two kinds of fluorinated polybenzimidazole (PBI)s which can be potentially used for phosphoric acid-doped, high-temperature polymer electrolyte membrane fuel cells. Two kinds of perfluorocyclobutane (PFCB)-containing monomers were prepared via following synthetic steps; after fluoroalkylation of methyl 3-(hydroxy) benzoate and methyl 4-(hydroxy) benzoate with 1,2-dibromotetrafluoroethane and subsequent Zn-mediated dehalogenation, these compounds were cyclodimerized at $200^{\circ}C$ affording the ester-terminated monomers containing PFCB ether groups. The synthesized intermediates and monomers were characterized using FT-IR, $^1H-NMR,\;^{19}F-NMR$, and mass spectroscopy. The fluorinated PBIs were then successfully prepared through the solution polycondensation of the monomers and 3,3'-diaminobenzidine in polyphosphoric acid. Compared with traditional PBI, the glass transition temperatures of the fluorinated PBIs were obtained at $262^{\circ}C\;and\;269^{\circ}C$ which are lower than that of PBI and their initial degradation temperatures were still high over $400^{\circ}C$ under nitrogen. The fluorinated PBIs showed higher d-spacing values and improved solubility in several organic solvents as well as phosphoric acid, which confirmed they could be good candidates for the high temperature fuel cell membranes.

• 멤브레인
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• 제31권3호
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• pp.228-240
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• 2021

알코올성 용제를 재활용할 수 있는 목적의 유기용제나노여과막(OSN)을 내용제성이 우수한 폴리벤지다졸 고분자를 이용하여 비용매 유도 상분리법을 이용하여 제조하였다. 제조한 나노여과막의 모폴로지와 투과특성을 조절하기 위하여 도프 용액의 농도와 물과 에탄올의 혼합용액인 응고액의 조성을 변화시키면서 제조하였다. α,α'-dibromo-p-xylene (DBX)을 이용하여 가교한 폴리벤지미다졸 분리막은 유기용제나노여과막으로 사용하기에 충분한 기계적 강도와 내용제성을 갖는 것을 확인하였다. 물로만 이루어진 응고조에서 도프용액의 농도가 20%이상인 분리막을 제조하는 경우에 분자량 696.66 g/mol을 가지는 콩고레드에 대한 제거율은 90% 이상을 나타내었고, 투과도는 5 bar의 압력에서 22.5 LMH/bar를 나타내었다. 응고액 조성에 대한 연구를 통해서 응고액 중의 에탄올 농도가 증가할수록 에탄올의 투과도가 증가하는 것을 확인하였다.

• Bulletin of the Korean Chemical Society
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• 제33권10호
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• pp.3279-3284
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• 2012

Poly(benzimidazole-co-benzoxazole)s (PBI-co-PBO) are synthesized by polycondensation reaction with 3,3'-diaminobenzidine, terephthalic acid and 3,3'-dihydroxybenzidine or 4,6-diaminoresorcinol in polyphosphoric acid (PPA). All polymer membranes are prepared by the direct casting method (in-situ fabrication). The introduction of benzoxazole units (BO units) into a polymer backbone lowers the basic property and $H_3PO_4$ doping level of the copolymer membranes, resulting in the improvement of mechanical strength. The proton conductivity of $H_3PO_4$ doped PBI-co-PBO membranes decrease as a result of adding amounts of BO units. The maximum tensile strength reaches 4.1 MPa with a 10% molar ratio of BO units in the copolymer. As a result, the $H_3PO_4$ doped PBI-co-PBO membranes could be utilized as alternative proton exchange membranes in high temperature polymer electrolyte fuel cells.

• 한국수소및신에너지학회논문집
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• 제18권4호
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• pp.439-445
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• 2007

Proton exchange membrane Fuel Cells(PEMFCs) have been spotlighted because of their broad potential application for potable electrical devices, automobiles and residential usages. However, their utilization is limited to low temperature operation due to the electrolyte dehydration at high temperature. High temperature PEMFC operation offers high CO tolerance and easy water management. This review presents development of high temperature($120{\sim}200^{\circ}C$) PEMFC. Especially, PEMFC which is based on acid-doped PBI membrane is discussed.

• 한국수소및신에너지학회논문집
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• 제26권2호
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• pp.127-135
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• 2015

High-Temperautre Polymer Electrolyte Membrane Fuel Cell (HT-PEMFC) with phosphoric acid-doped polybenzimidazole (PBI) membrane has high power density because of high operating temperature from 100 to $200^{\circ}C$. In fuel cell stack, heat is generated by electrochemical reaction and high operating temperature makes a lot of heat. This heat is caouse of durability and performance decrease about stack. For these reasons, heat management is important in HT-PEMFC. So, we developed HT-PEMFC model and study heat flow in HT-PEMFC stack. In this study, we placed coolant plate number per cell number ratio as variable and analysed heat flow distribution in stack.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2009년도 추계학술대회 논문집
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• pp.166-169
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• 2009

Poly(benzimidazole-co-aniline) (PBIANI), a self-crosslinked, net-structured, proton conducting polymer has been synthesized for the membrane of high temperature proton exchange membrane fuel cells (HT-PEMFC) with improved proton conductivity and mechanical strength. The stress at break (26$\pm$3MPa)and proton conductivity (167 mS cm-1)of the phosphoric acid doped PBIANI (DPBIANI)membrane is much higher than those of other doped polybenzimidazole(PBI) type membranes.

• Bulletin of the Korean Chemical Society
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• 제17권1호
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• pp.29-33
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• 1996

Mono-, or di-substituted chlorodicyanovinyl benzene compound was reacted with an excess amount of ethylenediamine to give corresponding imidazoline product with high reaction yield. This reaction occurs by stable imidazoline ring-forming process through nucleophilic attack of terminal amine on the enaminonitrile adduct, the reaction intermediate, toward electropositive enamine carbon, which is accompanied by the release of neutral malononitrile moiety. The similar reaction with 1,2-phenylenediamine produced stable enaminonitrile-amine adduct at lower temperature which could be cyclized intramolecularly to thermally stable benzimidazole at elevated temperature in solution or in solid state. From the difunctional compound of both reactants, poly(enaminonitrile-amine) could be prepared as a new soluble precursor polymer for well-known polybenzimidazole (PBI). The thermal cyclization reaction accompanying the release of malononitrile molecules was studied using thermalanalysis and infrared spectroscopy.

• 한국수소및신에너지학회논문집
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• 제28권5호
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• pp.471-480
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• 2017

A proton exchange membrane fuel cell (PEMFC) operated at $150^{\circ}C$ was evaluated by a controlling different amount of phosphoric acid (PA) to a membrane-electrode assembly (MEA) without humidification of the cells. The effects on MEA performance of the amount of PA in the cathode are investigated. The PA content in the cathodes was optimized for higher catalyst utilization. The highest value of the active electrochemical area is achieved with the optimum amount of PA in the cathode confirmed by in-situ cyclic voltammetry. The current density-voltage experiments (I-V curve) also shows a transient response of cell voltage affected by the amount of PA in the electrodes. Furthermore, this information was compared with the production variables such as hot pressing and vacuum drying to investigate those effect to the electrochemical performances.

• Membrane and Water Treatment
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• 제2권1호
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• pp.1-24
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• 2011

The deficiency of clean water is a major global concern because all the living creatures rely on the drinkable water for survival. On top of this, abundant of clean water supply is also necessary for household, metropolitan inhabitants, industry, and agriculture. Among many purification processes, advances in low-energy membrane separation technology appear to be the most effective solution for water crisis because membranes have been widely recognized as one of the most direct and feasible approaches for clean water production. The aim of this article is to give an overview of (1) two new emerging membrane technologies for water reuse and desalination by forward osmosis (FO) and membrane distillation (MD), and (2) the molecular engineering and development of highly permeable hollow fiber membranes, with polyvinylidene fluoride (PVDF) and polybenzimidazole (PBI) as the main focuses for the aforementioned applications in National University of Singapore (NUS). This article presents the main results of membrane module design, separation performance, membrane characteristics, chemical modification and spinning conditions to produce novel hollow fiber membranes for FO and MD applications. As two potential solutions, MD and FO may be synergistically combined to form a hybrid system as a sustainable alternative technology for fresh water production.

• 한국수소및신에너지학회논문집
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• 제29권5호
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• pp.442-449
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• 2018

Research on High temperature polymer electrolyte fuel cell (HT-PEMFC) has actively been conducted all over the world. Since the HT-PEMFC can be operated at a high temperature of $120-180^{\circ}C$ using phosphoric acid-doped polybenzimidazole (PBI) electrolyte membrane, it has considerable advantages over conventional PEMFC in terms of operating conditions and system efficiency. However, If the thermal distribution is not uniform in the stack unit, degradation due to local reaction and deterioration of lifetime are difficult to prevent. The thin plate separator reduces the volume of the fuel cell stack and improves heat transfer, consequently, enhancing the cooling effect. In this paper, a large area flow field of thin plate separator for HT-PEMFC is designed and sub-stack is fabricated. We have studied stack performance evaluation under various operating conditions and it has been verified that the proposed design can achieve acceptable stack performance at a wide operating range.