• 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.

• The Korean Journal of Ceramics
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• v.3 no.1
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• pp.52-56
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• 1997

The Pt doped $TiO_2$ composite membranes were prepared by the sol-gel process. The Pt doped titania sol was peptized with hydrochloric acid in the pH range of 1.23 to 1.32 at 5$0^{\circ}C$. The average particle size of the Pt doped titania sol was shown to be below 15nm and well dispersed in the solution. XPS show the Pt elements continuous and homogeneous dispersed in the $TiO_2$ membrane. The mean particle size of the Pt doped $TiO_2$ composite membrane has smaller than that of the undoped $TiO_2$ composite membrane. The average pore size of the Pt doped $TiO_2$ composite membrane was increased from 58 to 193 $\AA$ with firing temperature changed from 550 to 85$0^{\circ}C$. It was observed that the Pt doped $TiO_2$ composite membranes showed crack-free and homogeneous microstructue as well as narrow particle size distribution up to above 75$0^{\circ}C$.

• 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.

• 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.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.18 no.4
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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.

• 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.

• 한국전기화학회:학술대회논문집
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• 2005.07a
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• pp.83-86
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• 2005

• 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.