• 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.

• 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.

• 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.

• Journal of Electrochemical Science and Technology
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• v.9 no.3
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• pp.212-219
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• 2018

Perovskite type ceramic membranes which exhibit dual ion conduction (proton and oxygen ion conduction) can permeate water and can aid solving operational problems such as temperature gradient and carbon deposition associated with a working solid oxide fuel cell. From this point of view, it is crucial to reveal water transport mechanism and especially the nature of the surface sites that is necessary for water incorporation and evolution. $BaCe_{0.8}Y_{0.2}O_{3-{\alpha}}$ (BCY20) was used as a model proton and oxygen ion conducting membrane in this work. Four different catalytically modified membrane configurations were used for the investigations and water flux was measured as a function of temperature. In addition, CO was introduced to the permeate side in order to test the stability of membrane against water and $CO/CO_2$ and post operation analysis of used membranes were carried out. The results revealed that water incorporation occurs on any exposed electrolyte surface. However, the magnitude of water permeation changes depending on which membrane surface is catalytically modified. The platinum increases the water flux on the feed side whilst it decreases the flux on the permeate side. Water flux measurements suggest that platinum can block water permeation on the permeate side by reducing the access to the lattice oxygen in the surface layer.

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

• Membrane Journal
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• v.27 no.5
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• pp.389-398
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• 2017

The most important characteristic of the polymer electrolyte membranes (PEMs) for fuel cells, the proton conducting ability is mainly influenced by the distribution and morphology of the water channels inside the PEMs. Non-perfluorinated hydrocarbon PEMs are known to have weaker water channels than perfluorinated PEM, Nafion, and thus relatively low proton conducting ability. In this study, we used a mesoscale simulation technique to observe the water channel formation and phase separation behavior of hydrocarbon PEM, sulfonated polyimides, under the humidification condition. It was observed that the water molecules were distributed evenly through the entire hydrophilic region, and clear water clusters were formed only in the sulfonated polyimide having high sulfonation degree. In addition, it was observed that sulfonated polyimides have a difficulty in forming water channel under the low hydrated condition. These results clearly support the theories of the formation of water channels in non-perfluorinated hydrocarbon PEMs, and also well explain the tendency of proton conducting abilities of sulfonated polyimides. Thus, it is confirmed that mesoscale simulation techniques can be very effective in analyzing phase separation behavior and water channel formation in PEMs for fuel cells and elucidating the ion conducting abilities.

• Transactions of the Korean hydrogen and new energy society
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• v.22 no.1
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• pp.42-50
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• 2011

The Montmorillonite (MMT) in the polymer matrix is expected to reduce methanol permeability due to the tortous path formed by dispersed silicate layers. However, the polymer composite membranes containing non-proton conducting inorganic particle tend to show low proton conductivity. To solve this problem, we used an ion exchange method to prepare functionalized MMT with various silane coupling agents. The modified MMT was randomly dispersed in sulfonated poly (arylene ether sulfone) (SPAES) matrix to prepare SPAES/modified MMT composite membranes. The performances of hybrid membranes for DMFCs application were investigated. The SPAES/modified composite membrane showed increased proton conductivity compared with the non-modified MMT composite membrane. However, the methanol permeability of the SPAES/modified membrane was higher than that of the non-modified MMT.

• Membrane Journal
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• v.19 no.2
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• pp.89-95
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• 2009

A comb-like copolymer consisting of a poly(vinyl chloride) backbone and poly(hydroxy ethyl acrylate) side chains, i.e. PVC-g-PHEA, was synthesized through atom transfer radical polymerization (ATRP). This comb-like copolymer was crosslinked with 4,5-imidazole dicarboxylic acid (IDA) via the esterification of the -OH groups of PHEA in the graft copolymer and the -COOH groups of IDA. Upon doping with phosphoric acid (PA, $H_3PO_4$) to form imidazole-PA complexes, the proton conductivity of the membranes continuously increased with increasing PA content. A maximum proton conductivity of 0.011 S/cm was achieved at $100^{\circ}C$ under anhydrous conditions. The PVC-g-PHEA/IDA/PA complex membranes exhibited good mechanical properties, i.e. 575 MPa of Young's modulus, as determined by a universal testing machine (UTM). Thermal gravimetric analysis (TGA) shows that the membranes were thermally stable up to $200^{\circ}C$.

• Membrane Journal
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• v.30 no.1
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• pp.57-65
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• 2020

The purpose of this study was to compare the water channel morphology and the proton conductivity by changing the number of repeating units of the polymer backbone of PEMs, and to present a criterion for selecting an appropriate polymer model for MD simulation. In the model with the shortest polymer main chain, the movement of the main chain and the sulfonic acid group was observed to be large, but no change in the water channel morphology was found. In addition, due to the nature of the proton transport ability that is most affected by the water channel morphology, the proton conductivity did not show a significant correlation with the length of the polymer backbone. These results provide important information, particularly for the preparation of ionomers for binders. In general, a low molecular weight polymer electrolyte material is used for a binder ionomer. Since the movement of the main chain/sulfonic acid group is improved, it can play a role of enclosing the catalyst layer well. However, there is no change in its proton conducting performance. In conclusion, the preparation of ionomers for binders will require molecular weight and structure design with a focus on physical properties rather than proton transfer performance.

• Macromolecular Research
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• v.14 no.1
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• pp.101-106
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• 2006

The transport of reactant gas, electrons and protons at the three phase interfaces in the catalytic layers of membrane electrode assemblies (MEAs) in proton exchange, membrane fuel cells (PEMFCs) must be optimized to provide efficient transport to and from the electrochemical reactions in the solid polymer electrolyte. The aim of reducing proton transport loss in the catalytic layer by increasing the volume of the conducting medium can be achieved by filling the voids in the layer with small-sized electrolytes, such as dendrimers. Generation 1.5 and 3.5 polyamidoamine (PAMAM) dendrimer electrolytes are well-controlled, nanometer-sized materials with many peripheral ionic exchange, -COOH groups and were used for this purpose in this study. The electrochemically active surface area of the deposited catalyst material was also investigated using cyclic voltammetry, and by analyzing the Pt-H oxidation peak. The performances of the fuel cells with added PAMAM dendrimers were found to be comparable to that of a fuel cell using MEA, although the Pt utilization was reduced by the adsorption of the dendrimers to the catalytic layer.