• 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.

• Macromolecular Research
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• v.12 no.4
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• pp.413-421
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• 2004

Sulfonated poly(phthalazinone ether sulfone ketone) (SPPESK) membranes and sol-gel derived SPPESK/silica hybrid membranes have been investigated as potential polymer electrolyte membranes for direct methanol fuel cell (DMFC) applications. In comparison with the SPPESK membrane, the SPPESK/silica membranes exhibited higher water content, improved proton conductivity, and lower methanol permeability. Notably, the silica embedded in the membrane acted as a material for reducing the fraction of free water and as a barrier for methanol transport through the membrane. From the results of proton conductivity and methanol permeability studies, we suggest that the fractions of bound and free water should be optimized to obtain desirable proton conductivities and methanol permeabilities. The highly sulfonated PPESK hybrid membrane (HSP-Si) displayed higher proton conductivity (3.42 ${\times}$ 10$^2$ S/cm) and lower methanol permeability (4.15 ${\times}$ 10$\^$7/ $\textrm{cm}^2$/s) than those of Nafion 117 (2.54 ${\times}$ 10$^2$ S/cm; 2.36 ${\times}$ 10$\^$6/ $\textrm{cm}^2$/s, respectively) at 30$^{\circ}C$. This characteristic of the SPPESK/silica membranes is desirable for future applications related to DMFCs.

• Membrane Journal
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• v.16 no.3
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• pp.221-229
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• 2006

This study is about the preparation and characterization of sulfonated random copolymer membranes containing perfluorocyclobutane (PFCB), fluorenyl, and sulfonyl units. The polymers were prepared through three synthetic steps, that is, the synthesis of a trofluorovinylether-terminated monomer, its thermal polymerization, and post-sulfonation using chlorosulfonic acid. A series of sulfonated random copolymers with different ion exchange capacity (IEC) were prepared by changing contents of fluorenyl uints in polymers with fixed molar ratio of chlorosulfonic acid during the post-sulfonation reaction. All the synthesized compounds were characterized by FT-lR, $^1H-NMR$, $^{19}F-NMR$, and Mass spectroscopy. As the content of sulfonated fluorenyl units increased, the IEC, water uptake, and ion conductivity of the sulfonated random copolymer membranes increased. The sulfonated random copolymer S-1 and S-2 showed higher values of ion conductivity than the Nafion-115 in a wide range of temperatures ($25{\sim}80^{\circ}C$).

• 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.

• Transactions of the Korean hydrogen and new energy society
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• v.16 no.1
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• pp.40-48
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• 2005

Until recently, only perfluorinated ionomer membrane such as Nation and Aciflex practically could be successfully used in water splitting. However, these membrane are limited by high cost and loss of membrane performance such as proton conductivity at elevated temperature above 80$^{\circ}C$. The sulfonated aromatic polymers such as PEEK and PSf, polyimides, and polybenzimidazoles are expected to have lower production cost as well as satisfactory chemical and electrochemical properties. HPAs and sulfonated polymers could have a significant influence on water electrolysis performance at elevated temperatures above 80$^{\circ}C$, but these phenomena have received relatively little attention until now. Therefore, it would be desirable to investigate the interrelation between the HPA and sulfonated polymer, such as SPEEK. The SPEEK membrane were prepared by the sulfonation of PEEK, and HPA was blended with SPEEK to increase the mechanical strength and electrochemical characteristics. As a results, electrochemical characteristics such as proton conductivity and ion exchange capacity were improved with the addion of 0.5 g HPA. And the properties of polymer electrolyte, SPEEK/HPA were better than Nation membrane at elevated temperature above 80$^{\circ}C$.

• Transactions of the Korean hydrogen and new energy society
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• v.28 no.1
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• pp.17-23
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• 2017

Polyether ether ketone (PEEK) composite including tungstophosphoric acid(TPA) membranes have been intensively investigated for polymer electrolyte membrane water electrolysis (PEMWE) and thus covalently linked sulfonated polyether ether ketone (CL-SPEEK) with captured TPA composite membranes were prepared and characterized. Sulfonated polyether ether ketone (SPEEK) was prepared in sulfonation of PEEK and was cross-linked with 1,4 diiodobutane. The carbonyl group of SPEEK was reduced with $NaBH_4$ and 3-isocyanatepropyltriethoxysilane (ICPTES) was added. The TPA captured composite was prepared in reaction of TPA with 3-mercaptopropyltrime thoxysilane (MPTMS). The polymer composite membranes showed better thermostability and electrochemical properties than SPEEK. The membranes were prepared by sol-gel casting method. The polymer composite membrane featured 0.1285 S/cm of proton conductivity at $80^{\circ}C$ and outstanding durability.

• Transactions of the Korean hydrogen and new energy society
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• v.27 no.5
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• pp.478-484
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• 2016

Polyether ether ketone (PEEK) composite membranes have been intensively investigated for polymer electrolyte membrane water electrolysis (PEMWE). Covalently linked (CL) sulfonated polyether ether ketone (SPEEK) and cellulose polymer composite membranes were prepared and characterized. Polyether ether ketone (PEEK) and cellulose were sulfonated and then were covalently linked by 1,4-diiodobutane to produce covalently linked SPEEK and cellulose polymer composite membranes. The composite membranes showed better thermostability and electrochemical properties than SPEEK. The membranes were prepared by sol-gel casting method. CL-SPEEK/Cellulose composite membrane featured 0.2453 S/cm of proton conductivity at $80^{\circ}C$ which was better than that of Nafion.

• Proceedings of the Korean Powder Metallurgy Institute Conference
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• 2006.09a
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• pp.489-490
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• 2006

Branched sulfonated poly(ether sulfone-ketone) copolymer was prepared with bisphenol A, 4,4-difluorobenzophenone, sulfonated chlorophenyl sulfone (40mole% of bisphenol A) and THPE (1,1,1-tris-p-hydroxyphenylethane). THPE was used 0.4 mol% of bisphenol A to synthesize branched copolymers. Organic-inorganic nano composite membranes were prepared with copolymer and a series of $SiO_2$ nanoparticles (20 nm, 4, 7 and 10 wt%). The composite membranes were cast from dimethylsulfoxide solutions. The films were converted from the salt to acid forms with dilute hydrochloric acid. The membranes were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymers with water and methanol. Branched copolymer and nano composite membranes exhibit proton conductivities from $1.12{\times}10^{-3}$ to $6.04{\times}10^{-3}\;S/cm^2$, water uptake from 52.9 to 62.4%, IEC from 0.81 to 1.21 meq/g and methanol diffusion coefficients from $1.2{\times}10^{-7}$ to $1.5{\times}10^{-7}\;cm^2/S$.

• Journal of the Korean Electrochemical Society
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• v.18 no.2
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• pp.75-80
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• 2015

Multi-block sulfonated poly(arylene ether sulfone) (SPAES) copolymer was synthesized via nucleophilic aromatic substitution reaction for proton exchange membrane fuel cell application. After synthesizing the hydrophilic and hydrophobic precursor oligomers having different end-groups (F-terminated or OH-terminated), the effect of end group on the molecular weight was investigated. Hydrophilic oligomers with hydroquinone showed better performance as fuel cell membranes. SPAES membranes showed comparable proton conductivity to that of Nafion at $80^{\circ}C$ and above 70% RH. In particular, SPAES 9 with hydroquinone showed higher proton conductivity than SPAES 10 in the whole RH range studied. Increased local concentration of sulfonic acids within hydrophilic block might develop the hydrophilic-hydrophobic phase separation in the block copolymers.

• Transactions of the Korean hydrogen and new energy society
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• v.28 no.2
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• pp.144-149
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• 2017

A proton-conducting bisphenylpropaned sulfonated fluorinated blockcopolymer (BPSFBC) was synthesized. Five kinds of polymer electrolyted composite membranes were preparated by incorporating silica ($SiO_2$) with various weight ratio. And their characteristics were investigated by FT-IR (fourier transform infrared), $^1H-NMR$ ($^1H$ nuclear magnetic resonance), TGA (thermogravimetric analysis), water uptake, FE-SEM (field emission scanning electron microscopes), and ion conductivity properties. The water uptake and ion conductivity were increased until 9 wt% $SiO_2$, and then decreased. The maximum proton conductivity equal to $52mScm^{-1}$ was measured for the BPSFBC/$SiO_2$-9 composite membrane at $90^{\circ}C$ and 100% relative humidity. From the measured results, it is distinct that the manufactured composite membrane BPSFBC/$SiO_2$-9 can be considered as a polymer membrane suitable for a fuel cell electrolyte.