• Bulletin of the Korean Chemical Society
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• 제32권6호
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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.

• 한국수소및신에너지학회논문집
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• 제29권6호
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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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• 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.

• 한국표면공학회지
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• 제29권4호
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• pp.229-237
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• 1996

Porous matrices for PAFC were prepared with chemically synthesized polyaniline powders. Phosphoric acid doped polyaniline showed decreasing electric conductivities as the temperature increased. Above $100^{\circ}C$, it showed negligible conductivities. It was stable in phosphoric acid up to $250^{\circ}C$. SiC powders or SiC whiskers were added to polyaniline to decrease the thermal expansion of polyaniline. 10% of polytetrafluoroethylene(PTFE) was also added as a binder. The bubble pressures and wettabilities of matrices were investigated and compared with the porosities measured by porosimeter. Based on these data, the optimum manufacturing condition was determined. The bubble pressure of the matrix made by adding 25w/o SiC whiskers was 345mmHg, the wettability was 235w/o, and the porosity was 83%. In the unit cell operation, the performances of polyaniline matrices were as good as those of SiC matrices. This result suggested that polyaniline can be a possible candidate for the matrix material of PAFC.

• 한국수소및신에너지학회논문집
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• 제23권1호
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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.

• 조명전기설비학회논문지
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• 제27권6호
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• pp.95-99
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• 2013

Furnace is currently the most important doping process using POCl3 in solar cell. However furnace need an expensive equipment cost and it has to purge a poisonous gas. Moreover, furnace typically difficult appling for selective emitters. In this study, we developed a new atmospheric pressure plasma source, in this procedure, we research the atmospheric pressure plasma doping that dopant is phosphoric acid($H_3PO_4$). Metal tube injected Ar gas was inputted 5 kV of a low frequency(scores of kHz) induced inverter, so plasma discharged at metal tube. We used the P type silicon wafer of solar cell. We regulated phosphoric acid($H_3PO_4$) concentration on 10% and plasma treatment time is 90 s, 150 s, we experiment that plasma current is 70 mA. We check the doping depth that 287 nm at 90 s and 621 nm at 150 s. We analysis and measurement the doping profile by using SIMS(Secondary Ion Mass Spectroscopy). We calculate and grasp the sheet resistance using conventional sheet resistance formula, so there are 240 Ohm/sq at 90 s and 212 Ohm/sq at 150 s. We analysis oxygen and nitrogen profile of concentration compared with furnace to check the doped defect of atmosphere.

• 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.

• 한국고분자학회:학술대회논문집
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• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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• pp.184-184
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• 2006

We have succeeded in the preparation of high molecular weight polybenzimidazoles by solution polycondensation of 3,3'-diaminobenzidine tetrahydrochloride with isophthalic acid, terephthalic acid, or with their derivatives using polyphosphoric acid both as solvent and as condensing agent. Also, we modified phosphoric acid into fluoroalkyl-phosphonic acids[F-PA]. The main reasons are as follows, first of all F-PAs are stronger acids than PA and alkylphosphonic acids which should promote proton hopping and transport. In addition, F-PA has weaker adsorption onto Pt which help to prevent electrocatalyst poisoning and promote higher oxygen reduction activity. The ionic conductivity of 85%-H3PO4 doped membranes show $10^{-2}\;Scm^{-1}\;to\;3{\times}10^{-2}\;Scm^{-1}\;at\;150^{\circ}C$ MEA with 2 %-added electrolyte shows slightly higher cell voltage than the others.

• 한국수소및신에너지학회논문집
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• 제27권2호
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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.

• 전기화학회지
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• 제6권2호
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• pp.141-144
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• 2003

Proton conducting polymeric gels as the electrolytes of electrochemical capacitors have been prepared by two different methods: 1) swelling a polymethacrylate-based polymer matrix in aqueous solutions of inorganic and organic acids, and 2) polymerizing complexes of anhydrous acids and prepolymers with organic plasticizer. The FT-IR spectra strongly suggest that the carbonyl groups in the polymer matrix interact with protons from the doped acids. High ionic (proton) conductivity in the range of $6\times10^{-4}-4\times10^{-2}\;S\;cm^{-1}$ was obtained at room temperature for the aqueous gels. The non-aqueous polymer complexes showed rather low ionic conductivity, but it was about $10^{-3}\;S\;cm^{-1}\;at\;70^{\circ}C$ for the $H_3PO_4$ doped polymer electrolyte. The mechanisms of ion (proton) conduction in the polymeric systems are discussed.