• Korean Chemical Engineering Research
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• v.57 no.6
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• pp.768-773
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• 2019

The Fenton reaction, which evaluates the electrochemical durability of polymer membranes of polymer electrolyte fuel cells (PEMFC), and the degradation of polymer membranes by OCV holding method are compared. The Fenton reaction is a method that can evaluate the chemical durability of the polymer membrane at outside the cell in a shorter time than the OCV Holding method. The Fenton reaction was carried out at 30% hydrogen peroxide, 10 ppm iron, and $80^{\circ}C$ for 24 hours. OCV Holding was driven at $90^{\circ}C$, 30% relative humidity and OCV for 168 hours. The Fenton reaction caused a lot of degradation inside the polymer membrane. On the other hand, in OCV Holding, the membrane thickness was thinned by the entire surface and internal degradation. The fluorine emission rate was more than 10 times higher than that of OCV Holding due to the Fenton reaction. The hydrogen permeation rate increased about 30% at 24 hours of Fenton reaction. At OCV Holding, hydrogen permeability decreased after 24 hours and then increased. As a whole, there was a difference in a membranes deteriorated by Fenton reaction and OCV Holding.

• 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.

• Korean Chemical Engineering Research
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• v.58 no.1
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• pp.59-63
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• 2020

Radical scavenger is used to improve the durability of PEMFC polymer membrane. In this study, we investigated whether fucoidan extracted from seaweed as a radical scavenger prevents electrochemical degradation through Fenton and OCV Holding experiments. Fucoidan has an antioxidant effect, protecting the polymer membrane from hydrogen peroxide and oxygen radicals, reducing the degradation rate to 1/10. Fucoidan has been shown to be more effective than MnO₂, which is used as a radical scavenger. In the PEMFC cell, the accelerated durability evaluation method (OCV Holding) showed that fucoidan reduced the hydrogen permeability of the polymer membrane by 12% and enhanced the performance by 29.1% compared to without radical scavenger. And fucoidan was found to be more effective in the cathode side ionomer than the anode side.

• Korean Chemical Engineering Research
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• v.62 no.1
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• pp.1-6
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• 2024

As the demand for hydrogen electric vehicles for commercial vehicles increases, the durability of PEMFCs must increase more than five times that of passenger cars, so research and development to improve durability is urgent. When the PEMFC membrane electrode assembly (MEA) undergoes chemical degradation, the MEA thickness decreases and pinholes occur. In this study, changes in the performance and durability of the MEA were measured while increasing the clamping pressure of the unit cell after open circuit voltage (OCV) holding, an accelerated chemical degradation experiment. As the clamping pressure increased, the resistance of the polymer membrane and the membrane/electrode contact resistance decreased, improving the I-V performance and reducing the hydrogen permeability. As the hydrogen permeability decreased, the OCV increased. When the pinhole area was removed and the MEA clamping pressure was increased, the hydrogen permeability decreased sharply, confirming that the local degradation has a large effect on the performance and durability of the entire cell. When the pinhole was removed and re-clamping and OCV holding was evaluated, it was confirmed that the durability improved according to the decrease in membrane resistance and hydrogen permeability.

• Korean Chemical Engineering Research
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• v.57 no.3
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• pp.344-350
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• 2019

Durability is very important for the commercialization of membranes and electrode assemblies (MEA) developed for proton exchange membrane fuel cells (PEMFC). Durability evaluation of stationary PEMFC MEA has a problem that the voltage change rate should be measured for a long time over 1000 hours under constant current conditions. In this study, the electrochemical durability evaluation protocol of membranes (OCV holding method) using to vehicle MEAs was applied to the stationary MEA for the purpose of shortening the durability evaluation time. After operation of the stationary and automobile MEA for 168 hours under conditions of OCV, cathode oxygen, $90^{\circ}C$ and relative humidity of 30%, I-V, LSV, CV, impedance and FER were measured and compared. When the hydrogen permeability, OCV change, ionic conductivity, and fluorine flow rate, which represent the durability of the membrane after degradation, were all examined, it was shown that durability of stationary MEA membrane was better than that of vehicles MEA membrane. In addition, the electrode degradation of stationary MEA was smaller than that of vehicles MEA after degradation operation. It was possible to evaluate in a short time using automotive protocol that the durability of stationary MEA was superior that of vehicle MEA in terms of membrane and the electrode.

• Korean Chemical Engineering Research
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• v.60 no.1
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• pp.7-11
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• 2022

In the membrane forming process of a proton exchange membrane fuel cell (PEMFC), drying and annealing heat treatment processes are required for performance and durability. In this study, the optimal annealing temperature for improving the durability of the polymer membrane was studied. It was annealed in the temperature range of 125~175 ℃, and thermal stability and hydrogen permeability were measured as basic data of durability at each annealing temperature. The electrochemical durability was analyzed by Fenton reaction and open circuit voltage (OCV) holding. The annealing temperature of 165 ℃ was the optimal temperature in terms of thermal stability and hydrogen permeability. In the Fenton reaction, the fluorine emission rate of the membrane annealed at 165 ℃ was the lowest, and the lifespan of the membrane annealed at 165 ℃ was the longest in the OCV holding experiment, confirming that 165 ℃ was the optimal temperature for the durability of the polymer membrane.

• Korean Chemical Engineering Research
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• v.59 no.3
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• pp.339-344
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• 2021

In order to improve the PEMFC (Proton Exchange Membrane Fuel Cell) durability, it is important to accurately evaluate the durability of the membrane in a short time. Recently, DOE (Department of Energy) reported a protocol that combines the chemical and mechanical durability of membranes to evaluate them effectively. This protocol applies chemical/mechanical deterioration to the membrane by repeating wet/dry while OCV (Open Circuit Voltage) holding. The problem of this protocol is that it is highly affected by electrode degradation due to change cycles in OCV and that the evaluation time is long. By using oxygen instead of air as the cathode gas while leaving the other conditions of the DOE protocol as it is, the durability evaluation time could be reduced from 408 hours to 144 hours. By reducing the number of voltage change cycles to 1/3, the electrode degradation due to the voltage change cycle was reduced to 1/12 when oxygen was used compared to air at the end, thereby enabling more accurate evaluation of polymer membrane durability.

• Journal of Hydrogen and New Energy
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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.

• Korean Chemical Engineering Research
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• v.61 no.2
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• pp.189-195
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• 2023

As a PEMFC (Polymer Exchange Membrane Fuel Cell) cathode catalyst, Pt-Co/C has recently been widely used because of its improved durability. In a fuel cell, electrodes and electrolytes have a close influence on each other in terms of performance and durability. The effect on the electrochemical durability of the electrolyte membrane when Pt-Co/C was replaced in the Pt/C electrode catalyst was studied. The durability of Pt-Co/C MEA (Membrane Electrode Assembly) was higher than that of Pt/C MEA in the electrochemical accelerated degradation process of PEMFC membrane. As a result of analyzing the FER (Fluorine Emission Rate) and hydrogen permeability, it was shown that the degradation rate of the membrane of Pt-Co/C MEA was lower than that of Pt/C MEA. In the OCV (Open Circuit Voltage) holding process, the rate of decrease of the active area of the Pt-Co/C electrode was lower than that of the Pt/C electrode, and the amount of Pt deposited on the membrane was smaller in Pt-Co/C MEA than in Pt/C MEA. Pt inside the polymer membrane deteriorates the membrane by generating radicals, so the degradation rate of the membrane of Pt/C MEA with a high Pt deposition rate was higher than Pt-Co/C MEA. When the Pt-Co/C catalyst was used, the electrode durability was improved, and the amount of Pt deposited on the membrane was also reduced, thereby improving the electrochemical durability of the membrane.

• Korean Chemical Engineering Research
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• v.61 no.3
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• pp.362-367
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• 2023

Recently, research and development of proton exchange membrane fuel cells (PEMFC) membranes are progressing in the direction of thinning to reduce prices and improve performance. Demand for hydrogen-powered vehicles for commercial vehicles is also increasing, and their durability should be five times greater than those for passenger vehicles. Despite the thinning of the membranes, the durability of the membranes must be increased five times, so the improvement of the durability of the membranes has become more important. Since the acceleration durability evaluation time also needs to be shortened, the protocol using oxygen instead of air in the existing protocol was applied to a 10 ㎛ thin membrane to evaluate durability. The accelerated durability test (Open circuit voltage holding) was terminated at 720 hours. If the air-based department of energy (DOE) protocol was used, a lifespan of 450,000 km of driving hours would be expected, with a durability of about 1,500 hours. During the chemical durability evaluation, the active area of the electrode decreased by 51%, suggesting that catalyst degradation had an effect on membrane durability. Reducing the catalyst degradation rate is expected to increase membrane durability.