• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1902-1906
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• 2011

Sulfonated poly(fluorinated arylene ether)s (SDF-F)/poly[(N-vinylimidazole)-co-(3-methacryloxypropyl-trimethoxysilane)] (poly(VI-co-MPS))/poly(tetrafluoroethylene) (PTFE) is prepared for a high temperature proton exchange membrane fuel cell (PEMFC). The reaction of the membrane with phosphoric acid forms silicate phosphor, as a chemically bound proton carrier, in the membrane. Thus-formed silicate phosphor, nitrogen in the imidazole ring, and physically bound phosphoric acid act as proton carriers in the membrane. The physico-chemical and electrochemical properties of the membrane are investigated by various analytical tools. The phosphoric acid uptake and proton conductivity of the SDF-F/poly(VI-co-MPS)/PTFE membrane are higher than those of SDF-F/PVI/PTFE. The power densities of cells with SDF-F/poly(VI-co-MPS)/PTFE membranes at 0.6 V are 286, 302, and 320 mW $cm^{-2}$ at 150, 170, and 190 $^{\circ}C$, respectively. Overall, the SDFF/poly(VI-co-MPS)/PTFE membrane is one of the candidates for anhydrous HT-PEMFCs with enhanced mechanical strength and improved cell performance.

• Transactions of the Korean hydrogen and new energy society
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• v.29 no.6
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• pp.578-586
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• 2018

In this study, we prepared the modified PBI random copolymer to reduce the problems of the pristine PBI about low solubility and proton conductivity. The random copolymer was synthesized from suberic acid, 5-aminoisophthalic acid, and 3,3'-diaminobenzidine to obtain $X_1Y_9$, $X_1Y_1$, $X_9Y_1$. Then, the membrane was fabricated by using solvent casting method with methanesulfonic acid at $140^{\circ}C$. Subsequently, the membrane was doped with phosphoric acid at $40^{\circ}C$. The chemical structure of the polymers was characterized by FT-IR. In addition, the physiochemical properties of the PBI were investigated by TGA, oxidative stability, acid uptake. Finally, the proton conductivity was measured at $100-180^{\circ}C$ without humidification. As the result, $X_1Y_9$ PBI random copolymer membrane showed higher conductivity.

• Korean Membrane Journal
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• v.9 no.1
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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.

• 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.

• 한국신재생에너지학회:학술대회논문집
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• 2009.11a
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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.

• Transactions of the Korean hydrogen and new energy society
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• v.28 no.5
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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 Journal
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• v.16 no.4
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• pp.276-285
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• 2006

Acid-doped sulfonated poly(aryl ether benzimidazole) (S-PAEBI) copolymers were synthesized by a direct polymerization technique and a doping with phosphoric acid as a dopant, and the polymer electrolyte membranes were fabricated from them by a solution casting method. To optimize the reaction condition, the degree of sulfonation and doping level were varied in the ranges of $0{\sim}60%\;and\;0.7{\sim}5.7$, respectively. Physiochemical properties of the doped membranes were investigated by AFM, TGA and the measurement of proton conductivity. It was found that proton conductivities depend on doping levels of membranes. Conductivity determined at the condition of $130^{\circ}C$ and no humidity was $7.3{\times}10^{-2}S/cm$ for the $H_3PO_4$-doped PAEBI membrane with a doping level of 5.7.

• Transactions of the Korean hydrogen and new energy society
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• v.27 no.2
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• pp.144-154
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• 2016

HT-PEMFC (high temperature polymer electrolyte membrane fuel cell) using PA (phosphoric acid) doped PBI (polybenzimidazole) membrane has been researched for extending the lifetime. However, the existing work on durability of HT-PEMFC focuses on identifying degradation causes of lab scale. The short life time of HT-PEMFC is still the problem for its commercialization. In this paper, an operating method to maximize life time of 5kW HT-PEMFC stack are proposed. The proposed method includes major steps such as minimization of OCV (Open Circuit Voltage) exposure, control of the proper stack temperature, and N2 purging for the stack. This long life operating method was based on the fragmentary results of degradation from previous research works. Experimentally, the 5 kW homemade HT-PEMFC stack was operated for a long time based on the proposed method and the stack successfully can operate within the desired degradation rate for the target life time.

• Proceedings of the KAIS Fall Conference
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• 2004.06a
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• pp.96-99
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• 2004

A new proton conductive inorganic-organic hybrid membrane doped with $H_3PO_4$ was fabricated via sol-gel process wit 3- glycidoxypropyltrimethoxysilane(GPTMS), 3-aminopropyltriethoxysilane(APTES) and tetraethoxysilane(TEOS) asprecursors. Theproto conductivity of about 3.0$\times10^{-3}S/cm$ was obtained at $120^{\circ}C$ under $50\%$ relative humidity (R.H). DTA curves showed that the thermal stability of the membrane is significantly enhanced by the presence of $SiO_2$ framework up to $250^{\circ}C$. SEM and XRD revealed that the gel is microporou and amorphous. The addition of APTES improved the conductivity of the membranes and the effect of the APTES on the conductivity was also discussed in this paper.

• Transactions of the Korean hydrogen and new energy society
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• v.26 no.2
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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.