• Membrane Journal
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• v.29 no.5
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• pp.252-262
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• 2019

A sulfonated star branched poly(styrene-b-butadiene-b-styrene) triblock copolymer (SSBS) was synthesized with varying degrees of sulfonation. The effective sulfonation on the butadiene block was confirmed by FT-IR spectroscopy. Ion exchange capacity by titration was used to determine the degree of sulfonation. The synthesized polymer observed enhanced water uptake and proton conductivity. At room temperature, the SSBS with 25 mol% degree of sulfonation showed an outstanding proton conductivity of 0.114 S/cm, similar to that of commercial membrane, Nafion. The effect of temperature at constant relative humidity on conductivity resulted to a remarkable increase in proton conductivity. Methanol permeability studies showed a value lower than Nafion for all the sulfonated membranes. Structural nature observed using AFM showed that the membranes observed microphase separated nanostructures and the connectivity of the interionic channels.

• 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.16 no.2
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• pp.103-110
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• 2005

Proton conducting solid polymer electrolyte (SPE) membranes have been used in many energy technological applications such as water electolysis, fuel cells, redox-flow battery, and other electrochemical devices. The availability of stable membranes with good electrochemical characteristics as proton conductivity at high temperatures above 80 $^{\circ}C$ and low cost are very important for its applications. However, the presently available perfluorinated ionomers are not applicable because of high manufacturing cost and high temperature use to the decrease in the proton conductivity and mechanical strength. In order to make up for the weak points, the block copolymer (BPSf) of polysulfone and poly (phenylene sulfide sulfone) were synthesized and sulfonated. The electrolyte membranes were prepared with phosphotungstic acid (HPA)/sulfonated BPSf via solution blending. This study would be desirable to investigate the interaction between the HPA and sulfonated polysulfone. The results showed that the characteristics of SPSf/HPA blend membrane was a better than Nafion at high temperature, 100 $^{\circ}C$. These membranes proved to have a high proton conductivity, $6.29{\times}10-2$ S/cm, a water content, 23.9%, and a ion exchange capacity, 1.97 meq./g dry membrane. Moreover, some of the membranes kept their high thermal and mechanical stability.

• Membrane Journal
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• v.26 no.1
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• pp.1-13
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• 2016

Fuel cells are regarded as a representative energy source expected to replace fossil fuels particularly used in internal combustion engines. One of the most important components is polymer electrolyte membranes (PEMs) acting as a proton conducting barrier to prevent fuel gas crossover. Since water channels act as proton pathways through PEMs, many researchers have been focused on the 'good phase-separation of hydrophilic moiety' which ensures high water retention under low humidity enough to keep the water channel for good proton conduction. Here, we summarized the strategies which have been adopted to synthesize sulfonated PEMs having high proton conductivities even under low humidified conditions, and hope this review will be helpful to design high performance hydrocarbon PEMs.

• 한국신재생에너지학회:학술대회논문집
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• 2010.11a
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• pp.85.2-85.2
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• 2010

There is widespread effort to develop polymer membranes in place of Nafion for high temperature polymer electrolyte membrane fuel cell(PEMFC). In our study, SiO2 membranes are arranged by electrospinning method. For impregnation solution, the modified sulfonated poly(ether ether ketone)(SPEEK) polymer is prepared from sulfonation, sulfochlorination, partial reduction and lithiation reaction. The modified polymer is cross-linked with 1,4-diiodobetane in NMP solvent and then blended with Heteropoly acid(HPA). The characterization of membranes is confimed by FT-IR, Thermogravimetry(TGA), water uptake test and single cell performance test for PEMFC, etc. The composite membrane shows satisfactory thermal and mechanical properties. Beside, The membrane exhibits good ion exchange capacity and high proton conductivity. As a result, The composite membrane is promising as an alternative membrane in high temperature PEMFC.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.278-281
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• 2009

Proton exchange membrane is the key material for proton exchange membrane fuel cells (PEMFC). Currently widely-used perfluorosulfonic acid membranes have some disadvantages, such as low thermal stability, easy swelling, excessive crossover of methanol and high price etc. Other membranes, including sulfonated polymer, radiation grafted membranes, organic-inorganic hybrids and acid-base blends, do not satisfy the criteria for PEMFC, which set a barrier to the development and commercialization of PEMFC. Pore-filling type proton exchange membrane is a new proton exchange membrane, which is formed by filling porous substrate with electrolytes. Compared with traditional perfluorosulfonic acid membranes, pore-filling type proton exchange membranes have many advantages, such as non- swelling, low methanol permeation, high proton conductivity, low cost and a wide range of materials to choose. In this research, preparation methodology of pore-filling membranes by particularly using all hydrocarbon polymers and fuel cell performances with the membranes are evaluated.

• Membrane Journal
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• v.19 no.4
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• pp.291-301
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• 2009

Double-layered polymer electrolyte membranes were prepared from two different sulfonated poly(aryl ether sulfone) copolymers by the two-step solution casting method for direct methanol fuel cells (DMFC). Sulfonation degrees were adjusted 10% (SPAES-10) and 50% (SPAES-50) by controlling monomer ratios, and the weight ratios of SPAES-10 copolymer were varied in the range of 5~20% to investigate the effect of thickness of coating layers on the membranes. Proton conducting layers were fabricated from SPAES-50 solutions of N-methyl-2-pyrrolidone (NMP) by a solution casting technique, and coating layers formed on the semiliquid surface of the conducting layer by pouring of SPAES-10-NMP solutions onto. It was found that double-layered polymer electrolyte membrane could significantly reduce the methanol crossover through the membrane and maintain high proton conductivities being comparable to single-layered SPAES-50 membrane. The maximum power density of membrane-electrolyte assembly (MEA) at the condition of $60^{\circ}C$ and 2 M methanol-air was $134.01\;mW/cm^2$ for the membrane prepared in the 5 wt-% of SPAES-10 copolymer, and it was corresponding to the 105.5% of the performance of the commercial Nafion 115 membrane.

• Transactions of the Korean hydrogen and new energy society
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• v.28 no.5
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• pp.465-470
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• 2017

Sulfonated fluorinated block copolymers having diphenyl units were mixed with the sulfonated cationic conductive polymers at an optimum mixing ratio to form hybrid membranes for fuel cells and their characteristics were studied. 2D and 3D AFM topology analysis confirmed that the number of hydrophilic units in the hybrid membrane was improved. Through the FE-SEM, the microstructure of the hybrid membrane implied hydrogen bonding and pi-pi interactions, and EDAX confirmed carbon, oxygen, sulfur, and fluorine. The thermogravimetric analysis showed that the hybrid membrane was thermally stable and the hydrophilicity of the hybrid membrane was increased by the contact angle of water droplets. As a result, it was confirmed that the cation conductivity increased by a factor of 1.8 times as the number of acidic domains in the hybrid film increased.

• 한국전기화학회:학술대회논문집
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• 2005.07a
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• pp.307-312
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• 2005

• Bulletin of the Korean Chemical Society
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• v.34 no.6
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• pp.1763-1770
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• 2013

A series of the block copolymers were successfully synthesized from post-sulfonated hydrophilic and hydrophobic macromers via three-step copolymerization. The degrees of sulfonation (DS) of the copolymers (10%, 30%, or 50%) were controlled by changing the molar ratio of the hydrophilic and hydrophobic parts. The resulting block copolymers were characterized by $^1H$ NMR and other technologies. The membranes were successfully cast using dimethyl sulfoxide (DMSO) solution at $100^{\circ}C$. The copolymers were characterized to confirm chemical structure by $^1H$ NMR and FT-IR. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) demonstrated that all sulfonated block copolymers exhibited good thermal stability with an initial weight loss at temperatures above $240^{\circ}C$. The membranes showed acceptable ion exchange capacity (IEC) and water uptake values in accordance with DS. The maximum proton conductivity was 184 mS $cm^{-1}$ in block copolymer-50 at $60^{\circ}C$ and 100% relative humidity, while the conductivity of Nifion-115 was 160 mS $cm^{-1}$ under the same measurement conditions. AFM images of the block copolymer membranes showed well separated the hydrophilic and hydrophobic domains. From the observed results it is that the prepared block membranes can be considered as suitable polymer electrolyte membranes for the application of polymer electrolyte membrane fuel cells (PEMFC).