• Korean Chemical Engineering Research
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• v.47 no.4
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• pp.441-445
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• 2009

Effect of temperature on membrane degradation in PEMFCs was studied. After cell operation at different temperatures($60{\sim}90^{\circ}C$) under accelerating degradation conditions(OCV, anode dry, cathode RH 65%) for 144 h, cell performance decreased from 12 to 35%. The results of FER in effluent water showed that this decrease in cell performance was caused by membrane degradation by the attack of $H_2O_2$ or oxygen radicals(${\cdot}OH$, $HO_2{\cdot}$) and that resulted in increase in gas crossover for radical formation. Radical formation on the electrode was confirmed by ESR. Activation energy of 66.2 kJ/mol was obtained by Arrhenius plot used to analyze the effect of temperature on membrane degradation. Increase of cell temperature enhanced gas crossover rate, radical formation rate and membrane degradation rate.

• Korean Chemical Engineering Research
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• v.52 no.6
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• pp.695-700
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• 2014

Proton Exchange Membrane Fuel Cells (PEMFC) can generate hydrogen and oxygen from water by electrolysis. But the electrode and polymer electrolyte membrane degrade rapidly during PEM water electrolysis because of high operation voltage over 1.7V. In order to reduce the rate of anode electrode degradation, unsupported $IrO_2$ catalyst was used generally. In this study, Pt/C catalyst for PEMFC was used as a water electrolysis catalyst, and then the degradation of catalyst and membrane were analysed. After water electrolysis reaction in the voltage range from 1.8V to 2.0V, I-V curves, impedance spectra, cyclic voltammograms and linear sweep voltammetry (LSV) were measured at PEMFC operation condition. The degradation rate of electrode and membrane increased as the voltage of water electrolysis increased. The hydrogen yield was 88 % during water electrolysis for 1 min at 2.0V, the performance at 0.6V decreased to 49% due to degradation of membrane and electrode assembly.

• Korean Chemical Engineering Research
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• v.45 no.4
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• pp.345-350
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• 2007

During PEMFC operation, OCV(open circuit voltage) and low humidity conditions accelerate the degradation of perfluorosulfonic acid membrane. There have been no studies that clearly explain why these conditions accelerate the membrane degradation. In this study, the hydrogen permeability through the membrane, I-V polarization of MEA, fluoride emission rate(FER) and $H_2O_2$ concentration in condensed water were measured during cell operation under OCV and low relative humidity(RH). The experimental results were evaluated with oxygen radical mechanism the most commonly known for membrane degradation. It seems that low RH of anode is a good condition for $H{\cdot}$ radical formation on the Pt catalyst and the OCV condition accelerate the $H{\cdot}$ to form $HO_2{\cdot}$ radical attacking the polymer membrane.

• Korean Chemical Engineering Research
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• v.60 no.2
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• pp.217-222
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• 2022

It is very important to analyze the OCV change behavior during the open circuit potential holding (OCV holding) process, which accelerates the evaluation of the electrochemical durability of the PEMFC membrane. In this study, an empirical formula using the experimental data of three MEAs with different durability was created and compared. The durability evaluation time of the reinforced membrane MEA without radical scavenger inside the membrane was 383 h, and the durability evaluation time of the reinforced membrane MEA with radical scavenger inside the membrane was 1,000 and 1,650 h, respectively. The degradation of the membrane was divided into the reversible degradation that can be recovered by activation and the irreversible degradation that is not recovered. The irreversible degradation of the membrane was indicated by an increase in hydrogen permeability, and the change in hydrogen permeability was similar to the irreversible degradation constant c of all three MEAs. The initiation of irreversible deterioration without recovery is indicated by an increase in hydrogen permeability, and the OCV is not recovered due to an increase in hydrogen permeability, so the slope of the OCV recovery line (ORL) decreases, which can be confirmed by an increase in the constant c value of the empirical formula.

• Transactions of the Korean hydrogen and new energy society
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• v.23 no.3
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• pp.256-263
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• 2012

We studied the degradation phenomenon of Pt catalyst in PEMFC. We used the electron microscope analysis technique including the ultra-microtome pretreatment method, FEG-SEM and TEM analysis methods for analysis of Pt nanoparticles. The Pt catalyst degradation is observed not only in electrode site but also in membrane site. We investigated these various degradation phenomena. The cathode electrode layer thickness is reduced. The size of the catalyst is increased much larger than initial size in membrane site. The catalyst moved from electrode layer to the electrolyte membrane. The rounded shape of catalyst was changed to the polygon. As a result, we found that the catalyst degradation processes of migration and coarsening occurred by the followings mechanisms; (1) dissolution of Pt ; (2) diffusion of Pt ion ; (3) Pt ion chemical reduction in membrane; (4) Coarsening of Pt particles (Ostwald ripening) ; (5) polygon shape change of Pt by {111} plane growth.

• BMB Reports
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• v.33 no.6
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• pp.448-453
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• 2000

In yeast the key gluconeogenic enzyme, fructose-1,6-bisphosphatase (FBPase), is selectively targeted from the cytosol to the lysosome (vacuole) for degradation when glucose starved cells are replenished with glucose. The pathway for glucose induced FBPase degradation is unknown. To identify the receptor-mediated degradation pathway of FBPase, we investigated the presence of the FBPase receptor on the vacuolar membrane by cell fractionation experiments and binding assay using vid mutant (vacuolar import and degradation), which is defective in the glucose-induced degradation of FBPase. FBPase sedimented in the pellets from vid24-1 mutant after centrifugation at $15,000{\times}g$ for 15 min, suggesting that FBPase is associated with subcellular structures. Cell fractionation experiments revealed that FBPase is preferentially associated with the vacuole, but not with other organelles in vid24-1. FBPase enriched fractions that cofractionated with the vacuole were sensitive to proteinase K digestion, indicating that FBPase is peripherally associated with the vacuole. We developed an assay for the binding of FBPase to the vacuole. The assay revealed that FBPase bound to the vacuole with a Kd of $2.3{\times}10^6M$. The binding was saturable and specific. These results suggest that a receptor for FBPase degradation exists on the vacuolar membrane. It implies the existence of the receptor-mediated degradation pathway of FBPase by the lysosome.

• Korean Chemical Engineering Research
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• v.44 no.6
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• pp.597-601
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• 2006

The degradation of the Nafion membrane by oxygen radical (OH, $HO_2$) was investigated in Polymer electrolyte membrane fuel cell (PEMFC). Nafion membrane was degraded in Fenton solution consisted with hydrogen peroxide (10-30％) and ferrous ion (1-4 ppm) at $80^{\circ}C$. After degradation in Fenton solution, C-F, S-O and C-O chemical bonds of membrane were broken by oxygen radical attack. Breaking of C-F bond reduced the mechanical strength of Nafion membrane, and hence induced pinholes, resulting in increase of $H_2$ crossover through the membrane. Decomposition of S-O and C-O bonds decreased the ion exchange capacity of the electrolyte membrane. The performance of unit cell composed the membrane, which was degraded in 30％ $H_2O_2$ with 4ppm $Fe^{2+}$ solution for 48 hr, was about half times as low as one with normal membrane.

• Membrane Journal
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• v.17 no.3
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• pp.244-253
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• 2007

This research investigated the effect of a photocatalytic reaction on nanofiltration(NF) membrane fouling by natural organic matter(NOM). The photocatalytic degradation was very effective for destruction and transformation of NOM and was carried out by titanium dioxide($TiO_2$) and $TiO_2$-immobilized bead as a photocatalyst. In order to compare their phtocatalytic properties, the photocatalytic degradation of humic acid in the presence of calcium ion was used as a model reaction. After the photocatalytic degradation the membrane fouling was dramatically decreased.

• Korean Chemical Engineering Research
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• v.61 no.4
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• pp.517-522
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• 2023

A chemical/mechanical durability test of polymer membrane evaluation method is used in which air and hydrogen are supplied to the proton exchange membrane fuel cell (PEMFC) and wet/dry is repeated in the open circuit voltage (OCV) state. In this protocol, when wet/dry is repeated, voltage increase/decrease is repeated, resulting in electrode degradation. When the membrane durability is excellent, the number of voltage changes increases and the evaluation is terminated due to electrode degradation, which may cause a problem that the original purpose of membrane durability evaluation cannot be performed. In this study, the same protocol as the department of energy (DOE) was used, but oxygen was used instead of air as the cathode gas, and the wet/dry time and flow rate were also increased to increase the chemical/mechanical degradation rate of the membrane, thereby shortening the durability evaluation time of the membrane to improve these problems. The durability test of the Nafion 211 membrane electrode assembly (MEA) was completed after 2,300 cycles by increasing the acceleration by 2.6 times using oxygen instead of air. This protocol also accelerated degradation of the membrane and accelerated degradation of the electrode catalyst, which also had the advantage of simultaneously evaluating the durability of the membrane and the electrode.

• Korean Chemical Engineering Research
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• v.55 no.3
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• pp.296-301
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• 2017

Recently, there are many efforts focused on development of more economical non-fluorinated membranes for PEMFCs (Proton Exchange Membrane Fuel Cells). In this study, sulfonated poly (ether ether ketone) (sPEEK) membrane reinforced with poly imide was made to enhance of membrane durability. In order to test durability of single (un-reinforced) membrane and reinforced membrane MEA (Membrane and Electrode Assembly), degradation accelerated stress test was used. Before and after degradation, I-V polarization curve, hydrogen crossover current, electrochemical surface area, membrane resistance and charge transfer resistance were measured. As a result of experiments, hydrogen crossover current of reinforced MEA was lower than that of single MEA, therefor durability of reinforced MEA was higher than that of single MEA. There was not especially short phenomena in reinforced MEA after degradation accelerated stress test.