• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.58-59
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• 2006

Less than a decade ago, most alternate membrane materials for fuel cells relied upon a post-sulfonation process to generate ionic groups capable of transporting protons from the anode to the cathode. These random post sulfonations showed some promise, but in general they produced materials that were not sufficiently stable or protonically conductive at ion exchange capacities where aqueous swelling could be restricted. Our group began to synthesize disulfonated monomers that could be used to incorporate into random copolymer proton exchange membranes. The expected limitation was that the aromatic polymers might not be stable enough to withstand fuel cell conditions. However, this was mostly based upon an accelerated test known was the Fenton's Reagent Test, which did not seem to this author as being a reliable predictor of performance. A much better approach has been to evaluate the open circuit voltage (OCV) for alternate membranes, as well as the benchmark perfluorosulfonic acid systems. When this is done, the aromatic ionomers of this study, primarily based upon disulfonated polyarylene ether sulfones, show up quite well. Real time 3000 hours DMFC results have also been generated. Obtaining conductive materials at low humidities is another major issue where alternate membranes have not been particularly successful. In order to address this problem, multiblock copolymers with relatively high water diffusion coefficients have been designed, which show promise for conductivity at lowered humidity.

• Membrane Journal
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• v.24 no.4
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• pp.301-310
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• 2014

In this study, the silica nanoparticles were considerably chosen to improve a dimensional stability, proton transport and electrochemical performance of the resulting inorganic-organic nanocomposite membranes. For this purpose, hydrophobic silica (Aerosil$^{(R)}$ 812, Degussa) and hydrophilic silica (Aerosil$^{(R)}$ 380, Degussa) nanoparticles were, respectively, introduced into a Sulfonated poly(arylene ether sulfone) (SPAES) polymer matrix. The $SiO_2$ particles are evenly dispersed in a SPAES matrix by the aid of a non-ionic surfactant (Pluronics$^{(R)}$ L64). A $SiO_2$ content plays an important role in membrane microstructures and membrane properties such as proton conductivity and water uptake. Therefore, to study nanocomposite membranes with excessive amount of silica, the content of silica nanoparticles were increased up to 5 wt%. Interestingly, a hydrophobic $SiO_2$ containing nanocomposite membrane showed better electrochemical performance (29% higher than pristine SPAES) despite of low proton conductivity due to its adhesive properties with a catalyst layer in a single cell test. All the silica-SPAES membranes exhibited better performance than a pristine SPAES membrane.

• Macromolecular Research
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• v.17 no.5
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• pp.325-331
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• 2009

The synthesis and the characterization of crosslinked ABC triblock copolymer, i.e. polystyrene-b-poly (hydroxyethyl methacrylate)-b-poly(styrene sulfonic acid), (PS-b-PHEMA-b-PSSA) is reported. PS-b-PHEMA-b-PSSA triblock copolymer at 20:10:70 wt% was sequentially synthesized via atom transfer radical polymerization (ATRP). The middle block was crosslinked by sulfosuccinic acid (SA) via the esterification reaction between -OH of PHEMA and -COOH of SA, as demonstrated by FTIR spectroscopy. As increasing amounts of SA, ion exchange capacity (IEC) continuously increased from 2.13 to 2.82 meq/g but water uptake decreased from 181.8 to 82.7%, resulting from the competitive effect between crosslinked structure and the increasing concentration of sulfonic acid group. A maximum proton conductivity of crosslinked triblock copolymer membrane at room temperature reached up to 0.198 S/cm at 3.8 w% of SA, which was more than two-fold higher than that of Nafion 117(0.08 S/cm). Transmission electron microscopy (TEM) analysis clearly showed that the PS-b-PHEMA-b-PSSA triblock copolymer is microphase-separated with a nanometer range and well developed to provide the connectivity of ionic PSSA domains. The membranes exhibited the good thermal properties up to $250^{\circ}C$ presumably resulting from the microphase-separated and crosslinked structure of the membranes, as revealed by thermal gravimetric analysis (TGA).

• Transactions of the Korean hydrogen and new energy society
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• v.30 no.3
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• pp.227-236
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• 2019

In this work, preparation and characterizations of hybrid membranes containing sulfonated poly(arylene ether sulfone) (SPES) and sulfonated poly(vinylidene fluoride-co-hexafluoropropylene) (SPVdF-co-HFP) (20, 30 or 40 wt%) were carried out. The structure of hybrid membranes was confirmed using X-ray diffraction (XRD) analysis and the Fourier transform infrared (FT-IR) spectroscopy. The prepared SPAES/SPVdF-30 membrane exhibits higher ionic conductivity of 68.9 mS/cm at $90^{\circ}C$ and 100% RH. Besides, the other studies showed that the hybrid membrane has good oxidation stability, thermal stability, and mechanical stability. Thus, we believe that the prepared hybrid membrane is suitable for the development of membranes for fuel cell applications.

• Transactions of the Korean hydrogen and new energy society
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• v.27 no.6
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• pp.660-669
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• 2016

A fluorinated-sulfonated, hydrophobic-hydrophilic copolymer was planed subsequently synthesized using typical nucleophilic substitution polycondensation reaction. A novel AB and ABA (or BAB) block copolymers were synthesized using sBCPSBP (sulfonated 4,4'-bis[4-chlorophenyl)sulfonyl]-1,1'-biphenyl), DHN (1,5-dihydroxynaphthalene), DFBP (decafluorobiphenyl) and HFIP (4,4'-hexafluoroisopropylidenediphenol). All block copolymers were easily cast and made into clear films. The structure and synthesized copolymers and corresponding membranes were analyzed using GPC (gel permeation chromatography), $^1H$-NMR ($^1H$ nuclear magnetic resonance) and FT-IR (Fourier transform infrared). TGA (Thermogravimetric analysis) and DSC (differential scanning calorimetry) analysis showed that the prepared membranes were thermally stable, so that elevated temperature fuel cell operation would be possible. Hydrophobic/hydrophilic phase separation and clear ionic aggregate block morpology was confirmed in both triblock and diblock copolymer in AFM (atomic force microscopy), which may be highly related to their proton transport ability. A sulfonated BAB triblock copolymer membrane with an ion-exchange capacity (IEC) of 0.6 meq/g has a maximum ion conductivity of 40.3 mS/cm at $90^{\circ}C$ and 100% relative humidity.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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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.

• Proceedings of the Korean Fiber Society Conference
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• 2003.10b
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• pp.34-37
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• 2003

The development and improvement of advanced fuel cell systems is a major topic of current research, since fuel cells are considerably more efficient than other energy converters$^1$. In proton exchange membrane fuel cell and direct methanol fuel cell the polymer membrane represents a key component. The membrane materials fulfill complex requirements. It has to combine electrochemical stability, workability, high ionic conductivity, low permeation of the reactants (methanol etc.) (omitted)

• Journal of the Korean Ceramic Society
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• v.32 no.12
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• pp.1357-1368
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• 1995

Nasigels of composition Na0.75Zr2PSi2O12 and Na3Zr2PSi2O12 have been synthesized by the sol-gel technique using metal alkoxide precursors. The monolithic dry gels of Na0.75Zr2PSi2O12 with no crack have been prepared by the control of the shrinkage rte, but gels of Na3Zr2PSi2O12 were impossible to prepare without cracking. The gels treated up to 80$0^{\circ}C$ led to the formtion of glass but the glasses were converted to the crystalline phases at above this temperature. Crystaline phases precipitated from the Na0.75Zr2PSi2O12 glass were NASICON-like phase, Na2Si2O5, and free Zirconia. Phase that precipitated from the Na3Zr2PSi2O12 was only rhombohedral NASICON. For Na0.75Zr2PSi2O12 gels, framework of PO4 tetrahedra and SiO4(PO4) tetrahedra formed at low temperature but changed to that of SiO4 and SiO4(PO4) tetrahedras as it were crystallized. In the case of Na3Zr2PSi2O12 gel, framework of isolated PO4 and SiO4 tetrahedras formed at low temperature but changed to SiO4(PO4) tetrahedra framework which usually formed in the NASICON crystal after crystallization at high temperature. The gels treated up to 80$0^{\circ}C$ contained the residual water. The ionic conduction was attributed to the motion of proton and Na+ ion at low (up to 150~20$0^{\circ}C$) and high temperatures, respectively. As the temperature of heat treatment increased, ionic conductivity gradaully increased with the extent of precipitation of crystalline phase.

• Polymer(Korea)
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• v.36 no.2
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• pp.155-162
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• 2012

Sulfonated poly(ether ether ketone) (SPEEK) nanofibers were prepared by electrospinning. The nanofibrous membrane for polymer electrolyte membrane fuel cell (PEMFC) was fabricated by compression molding. The maximum degree of sulfonation was 95% and the initial thermal degradation temperature was $280^{\circ}C$ and it's value was lower than that of PEEK. The contact angle of SPEEK increased with decreasing the degree of sulfonation. The optimum voltage, flow rate, tip to collector distance (TCD) and concentration of electrospinning conditions were 22 kV, 0.3 mL/hr, 15 cm, and 23 wt%, respectively. The average nanofibrous diameter was 47.6 nm. The water uptake and ion exchange capacity of SPEEK nanofibrous membrane increased with increasing the sulfonation time and the amount of sulfonating agent. The electrical resistance and proton ionic conductivity of SPEEK membrane increased with decreasing and increasing the sulfonation time, respectively. Their values were 0.58~0.06 ${\Omega}{\cdot}cm^2$and 0.099 S/cm.

• Journal of the Korean Ceramic Society
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• v.47 no.1
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• pp.82-85
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• 2010

Recently, thin film processes for oxides and metal deposition, such as physical vapor deposition (PVD) and chemical vapor deposition (CVD), have been widely adapted to fabricate solid oxide fuel cells (SOFCs). In this paper, we presented two research area of the use of such techniques. Gadolinium doped ceria (GDC) showed high ionic conductivity and could guarantee operation at low temperature. But the electron conductivity at low oxygen partial pressure and the weak mechanical property have been significant problems. To solve these issues, we coated GDC electrolyte with a nano scale yittria-doped stabilized zirconium (YSZ) layer via atomic layer deposition (ALD). We expected that the thin YSZ layer could have functions of electron blocking and preventing ceria from the reduction atmosphere. Yittria-doped barium zirconium (BYZ) has several orders higher proton conductivity than oxide ion conductor as YSZ and also has relatively high chemical stability. The fabrication processes of BYZ is very sophisticated, especially the synthesis of thin-film BYZ. We discussed the detailed fabrication processes of BYZ as well as the deposition of electrode. This paper discusses possible cell structure and process flow to accommodate such films.