• 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.

• 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.

• Journal of the Korean Applied Science and Technology
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• v.22 no.2
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• pp.151-156
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• 2005

Many researchers have been focused on polymer electrolyte membrane (PEM) to improve performance of a fuel cell. Sulfonpolyimide with hydrocarbon was synthesized from ODA (4,4-diaminodiphenyl ether), ODADS (4,4-diaminodiphenyl ether-2,2-disulfonic acid), NTDA (1,4,5,8-naphthalenetetracarboxylicdianhydride) and CSA (chlorosulfonic acid). In order to estimate the feasibility as a fuel cell, the performance of sulfonpolyimide was analyzed through a swelling degree, IEC (ion exchange capacity), ion conductivity and TEM (transmission electron microscope). As the results of this performance test, swelling degree, IEC and ion conductivity were 37%, 0.06 meq/g and 0.08 S/cm respectively, when the CSA concentration was 0.4 M. It was thought that sulfonpolyimide could be used as a fuel cell through improvement of electrolyte membrane.

• Journal of the Korean Electrochemical Society
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• v.19 no.2
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• pp.39-44
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• 2016

Oxygen reduction reaction in the fuel cell (ORR) plays a dominant role in the overall reaction. In addition, the low compatibility between the membrane and the binder consisted of different materials, greatly reduces the efficiency of the fuel cell performance. In view of these two problems, geometrically modified copolymers with 9.9_Bis (4-hydroxyphenyl) were synthesized via condensation reaction instead of conventional biphenol and were adopted as hydrocarbon ionomer binders. By utilizing these binders, two kinds of MEAs using fluorinated Nafion membrane and hydrocarbon based membrane were manufactured in order to electrochemical performance evaluation. With current-voltage curves, there was no significant difference in the 0.6 V when two types of membrane were applied. Also, tafel slope became considerably lower as compared to the Nafion membrane. Thus, it is determined that the new hydrocarbon binder is expected to contribute the improvement in performance of fuel cells.

• 한국신재생에너지학회:학술대회논문집
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• 2005.06a
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• pp.235-238
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• 2005

Sulfonated poly(ether sulfone) copolymers (PESs) were synthesized using hydroquinone 2-potassium sulfonate (HPS) with other monomers (bisphenol A and 4-fluorophenyl sulfone). PESs with different $mole\%$ of hydrophilic group were prepared by changing the mole ratio of HPS in the polymerization reaction. The chemical structure and the thermal stability of these polymers were characterized by using $^1H-NMR$, FT-IR and TGA techniques. The PES 60 membrane, which has $60 mole\%$ of HPS unit in the polymer backbone, has a proton conductivity of 0.091 S/cm and good insolubility in boiling water. The TGA showed that PES 60 was stable up to $272^{\circ}C$ with a char yield of about $29\%\;at\;900^{\circ}C\;under\;N_2$ atmosphere. To investigate the single cell performance, the catalyst coated PES 60 membrane was used and a single cell test was carried out using $H_2/O_2$ gases as fuel and oxidant at various temperatures. We observed that the cell performance was enhanced by increasing the cell temperature. A current density of $1400 mA/cm^2$ at 0.60 V was obtained at $70^{\circ}C$.

• Membrane Journal
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• v.33 no.3
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• pp.127-136
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• 2023

In this study, the electrochemical performance of a 5-layer fuel cell stack using silica composite membranes as polymer electrolyte membranes was evaluated. It was observed that the flow rate of the fuel gases plays a crucial role in stack performance, particularly being mainly dependent on the flow rate of hydrogen. Increasing the flow rate of oxygen resulted in negligible changes in performance, whereas an increase in the flow rate of hydrogen demonstrated performance improvements. However, this led to an imbalance in the ratio of hydrogen to oxygen flow rates, causing significant degradation in stack performance and durability. A decline in stack performance was also observed over time due to the degradation of stack components. This phenomenon was consistently observed in individual unit cells. Based on these findings, it was emphasized that, in addition to optimizing the performance of each component during stack operation, it is important to optimize design and operating conditions for uniform flow rate control. Lastly, the developed silica composite membrane was assessed to have sufficient performance for application in actual fuel cell systems, exhibiting a performance of over 25 W based on maximum power.

• Membrane Journal
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• v.27 no.2
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• pp.182-188
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• 2017

Sulfonated poly(arylene ether sulfone) (SPAES)-3-mercaptopropyl silica gel (3MPTSG) composite membranes with improved oxidative stability were prepared for polymer electrolyte fuel cell application. It has been reported that ether part of main chain of aromatic hydrocarbon based membranes were weak to radical attack to decrease membrane durability. In this study, the hydrophilic inorganic particles were introduced by minimizing a decrease in ion conductivity and increasing an oxidative stability. The composite membranes were investigated in terms of ionic conductivity, ion exchange capacity (IEC), FT-IR, TGA and contact angle, etc. As a result, increasing amount of the 3MPTSG resulted in decrease in proton conductivities and water uptakes at 100% R.H. but enhanced thermal and oxidative stabilities.

• Membrane Journal
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• v.25 no.5
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• pp.456-463
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• 2015

In this study, we synthesize novel silane based inorganics for preparation of the polymer electrolyte membrane with high proton conductivity under high temperature condition and developed membranes are characterized. SPAES, hydrocarbon based polymer are synthesized and used as main polymeric material. We used sol-gel method to prepare inorganic material with high performance using silica, phosphate and zirconium. Three types of inorganics were prepared by control of the mole ration of each component. As a result of EDX analysis, the inorganic materials are well dispersed in the polymer membrane. The water uptake of the composite membrane is increased by introduction of the hydrophilic inorganic material in the membrane. When the content of the zirconium in the membrane is increased, the proton conductivity of the composite membrane shows the higher value than pure SPAES membrane at the high temperature. And the silica based inorganics effect to increase the proton conductivity under low temperature condition.

• Transactions of the Korean hydrogen and new energy society
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• v.34 no.6
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• pp.673-681
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• 2023

Hydrocarbon-based polymer membranes to replace perfluorinated polymer membranes are being continuously researched. However, hydrocarbon-based membranes have a problem in that they are less durable than fluorine-based membranes. In this study, we sought to compare the annealing effect to improve the durability of sulfonated poly(ether ether ketone) (SPEEK). After membranes formation, thermogravimetric analysis and tensile strength were measured to compare changes in membranes properties due to annealing. After manufacturing the membrane and electrode assembly (MEA), the initial performance and chemical durability was compared with unit cell operation. During the 24-hour annealing process, the strength increased due to the increase in-S-O-S-crosslinking, and the sulfonic acid group decreased, leading to a decrease in I-V performance. By annealing, the hydrogen permeability was reduced to less than 1/10 of that of the nafion membrane, and as a result, open circuit voltage (OCV) and durability was improved. The SPEEK membranes annealed for 24 hours showed higher durability than the nafion 211 membranes of the same thickness.