• Bulletin of the Korean Chemical Society
• /
• v.31 no.8
• /
• pp.2141-2142
• /
• 2010

• Transactions of the Korean hydrogen and new energy society
• /
• v.29 no.4
• /
• pp.331-338
• /
• 2018

In this study, sulfonated PAES block copolymers have been synthesized via nucleophilic substitution reaction. Hydrophobic oligomer was prepared using 2,6-dihydroxynaphthalene and bis(4-chlorophenyl) sulfone, whereas hydrophilic oligomer was prepared using sulfonated bis(4-chlorophenyl) sulfone and bis(4-hydroxyphenyl) sulfone. The chemical structure of polymers was analyzed by $^1H$ NMR, FT-IR and GPC. The thermal properties of polymers were measured by TGA and DSC. The oxidative stability of membranes was investigated by Fenton's test. Furthermore, the proton conductivity of membrane was found to be 26 mS/cm at $90^{\circ}C$. All physiochemical properties suggest that fabricated membrane have a great potential for applications in PEMFC.

• 한국신재생에너지학회:학술대회논문집
• /
• 2010.11a
• /
• pp.75.2-75.2
• /
• 2010

Polymer electrolyte fuel cells (PEFCs) have received a lot of attention as a power source for both stationary and mobile applications due to their attractive feature. In general, the performance of PEFCs is highly affected by the property of the electrodes. A PEFC electrode essentially consists of a gas diffusion layer and a catalyst layer. The gas difusion layer is highly porous and hydrophobicized with PTFE polymer. The catalyst layer usually contains electrocatalyst, proton conducting polymer, even PTFE as additive. Particularly, the proton conducting ionomer helps to increase the catalytic activity at three-phase boundary and catalyst utilization. Futhermore, it helps to retain moisture, resulting in preventing the electrodes from membrane dehydration. The most widely used proton conducting ionomer is perfluorinated sulfonic acid polymer, namely, Nafion from DuPont due to its high proton conductivity and good mechanical property. However, there are great demands for alternative ionomers based on non-fluorinated materials in terms of high temperature availability, environmental adaptability and production cost. In this study, the electrodes with the various content of the sulfonated poly(ether sulfone) ionomer in the catalyst layer were prepared. In addition, we evaluated electrochemical properties of the prepared electrodes containing the various amount of the ionomers by using the cyclic voltammetry and impedance spectroscopy to find an optimal ionomer composition in the catalyst layer.

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

• Proceedings of the Polymer Society of Korea Conference
• /
• 2006.10a
• /
• pp.185-185
• /
• 2006

The performances of proton exchange membrane fuel cell (PEMFC), direct formic acid fuel cell (DFAFC) and direct methanol fuel cell (DMFC) with sulfonated poly(ether sulfone) membrane are reported. Pt/C was coated on the membrane directly to fabricate a MEA for PEMFC operation. A single cell test was carried out using $H_2/air$ gases as fuel and oxidant. A current density of $730\;mA/cm^2$ at 0.60 V was obtained at $70^{\circ}C$. Pt-Ru (anode) and Pt (cathode) were coated on the membrane for DMFC operations. It produced $83\;mW/cm^2$ of maximum power density. The sulfonated poly(ether sulfone) membrane was also used for DFAFC operation under several different conditions. It showed good cell performances for several different kinds of polymer electrolyte fuel cell applications.

• Proceedings of the Korean Powder Metallurgy Institute Conference
• /
• 2006.09a
• /
• pp.489-490
• /
• 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 $1.5{\times}10^{-7}\;cm^2/S$.

• Membrane Journal
• /
• v.22 no.3
• /
• pp.191-200
• /
• 2012

New composite membranes were manufactured by impregnating post-sulfonated poly(arylene ether sulfone)s containing perfluorocyclobutane (PFCB) groups into porous polytetrafluoroethylene (PTFE) films. Two kinds of post-sulfonated poly(arylene ether sulfone)s with two different monomer ratios (sulfonable biphenylene monomer : non-sulfonable sulfonyl monomer = 6 : 4, 4 : 6) were first prepared through three synthetic steps: synthesis of trifluorovinylether-terminated monomers, thermal cycloaddition polymerization and post-sulfonation using chlorosulfonic acid (CSA). The composite membranes were then prepared by adjusting the concentrations (5~20 wt%) of the resulting copolymers impregnated in the PTFE films. The water uptake, ion exchange capacity (IEC) and ion conductivity of the composite membranes were characterized and compared with their unreinforced dense membranes and Nafion. All the synthesized compounds, monomers and polymers were characterized by $^1H$-NMR, $^{19}F$-NMR and FT-IR and the composite membranes were observed with scanning electron micrographs (SEM).

• Polymer(Korea)
• /
• v.34 no.2
• /
• pp.137-143
• /
• 2010

A series of partially fluorinated, sulfonated poly(biphenylene-co-sulfone)ether containing perfluorocyclobutane(PFCB) groups were prepared for fuel cell applications through three synthetic steps: synthesis of trifluorovinylether-terminated monomers, thermal cycloaddition and post-sulfonation. Two kinds of trifluorovinylether-terminated monomers were synthesized and statistically copolymerized via thermal cycloaddition to obtain a series of polymers containing 20-60 mol% of biphenyl units(PBS-X). The post-sulfonation of PBS-X was carried out using chlorosulfonic acid(CSA) to obtain copolymers with various sulfonation levels(SPBS-X). All the synthesized compounds, monomers and polymers were characterized by $^1H$-NMR, $^{19}F$-NMR and FT-IR. It was confirmed that the ion exchange capacity(IEC), water uptake and ion conductivity of SPBS-X increased with the increment of sulfonated biphenyl units. Particularly, SPBS-60 showed higher ion conductivity compared to Nafion$^{(R)}$-115 at 25~80 $^{\circ}C$.

• Journal of the Korean Electrochemical Society
• /
• v.11 no.4
• /
• pp.256-261
• /
• 2008

In this study, Nafion membrane was modified to prevent methanol crossover by layer-by-layer self assembly using polyaniline (PANi) as a polycation and sulfonated poly(ether sulfone) (SPES) as a polyanion onto the Nafion surface. Since PANi and SPES possess thermal and chemical stability and rigid backbone, their layer-by-layer self-assembled films on the Nafion are expected to reduce methanol permeability and to increase mechanical stability. UV-Vis absorption spectroscopy verified a linear build-up of the multilayers of PANi and SPES. We found that the thickness per bilayer was about 10 nm by TEM measurement. Although modified Nafion membrane exhibited 15% decrease of proton conductivity, it reduceded 67% of methanol permeability compared to that of the pristine Nafion membrane, resulting in 2.5 times larger selectivity. At the performance test of the fuel cell using 5M methanol as a fuel, the modified Nafion membrane showed 2.4 times higher maximum power density at $30^{\circ}C$ and 1.4 times larger at $60^{\circ}C$ than the pristine Nafion.

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