• 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.

• 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.

• Membrane Journal
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• v.33 no.6
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• pp.325-343
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• 2023

Direct methanol fuel cells (DMFCs) have been attracting attention as energy conversion devices that can directly supply methanol liquid fuel without a fuel reforming process. The commercial polymer electrolyte membranes (PEMs) currently applied to DMFC are perfluorosulfonic acid ionomer-based PEMs, which exhibit high proton conductivity and physicochemical stability during the operation. However, problems such as high methanol permeability and environmental pollutants generated during decomposition require the development of PEMs for DMFCs using novel ionomers. Recently, studies have been reported to develop PEMs using hydrocarbon-based ionomers that exhibit low fuel permeability and high physicochemical stability. This review introduces the following studies on hydrocarbon-based PEMs for DMFC applications: 1) synthesis of grafting copolymers that exhibit distinct hydrophilic/hydrophobic phase-separated structure to improve both proton conductivity and methanol selectivity, 2) introduction of cross-linked structure during PEM fabrication to reduce the methanol permeability and improve dimensional stability, and 3) incorporation of organic/inorganic composites or reinforcing substrates to develop reinforced composite membranes showing improved PEM performances and durability.

• Membrane Journal
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• v.30 no.6
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• pp.395-408
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• 2020

Polymer electrolyte membrane fuel cells (PEMFCs) have gained much attention as eco-friendly energy conversion devices without emission of environmental pollutant. Polymer electrolyte membrane (PEM) that can transfer proton from anode to cathode and also prevent fuel cross-over has been regarded as a key component of PEMFCs. Although perfluorinated polymer membranes such as Nafion® were already commercialized in PEMFCs, their high cost and toxic byproduct generated by degradation have still limited the wide spread of PEMFCs. To overcome these issues, development of hydrocarbon based PEMs have been studied. Incorporation of cross-linked structure into the hydrocarbon based PEM system has been reported to fabricate the PEMs showing both high proton conductivity and outstanding physicochemical stability. This study focused on the various cross-linking strategies to the preparation of cross-linked PEMs based on hydrocarbon polymers with ion conducting groups for application in PEMFCs.

• Membrane Journal
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• v.32 no.6
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• pp.427-441
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• 2022

Polymer electrolyte membrane (PEM) serving as a separator that can prevent the permeation of unreacted fuels as well as an electrolyte that selectively transports protons from the anode to the cathode has been considered a key component of polymer electrolyte membrane fuel cell (PEMFC). The perfluorinated sulfonic acid-based PEMs, represented by Nafion®, have been commercialized in PEMFC systems due to their high proton conductivity and chemical stability. Nevertheless, these PEMs have several inherent drawbacks including high manufacturing costs by the complex synthetic processes and environmental problems caused by producing the toxic gases. Although numerous studies are underway to address these drawbacks including the development of sulfonated hydrocarbon polymer-based PEMs (SHP-PEMs), which can easily control the polymer structures, further improvement of PEM performances and durability is necessary for practical PEMFC applications. Therefore, this study focused on the various strategies for the development of SHP-PEMs with outstanding performance and durability by 1) introducing cross-linked structures, 2) incorporating organic/inorganic composites, and 3) fabricating reinforced-composite membranes using porous substrates.