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Increased Chemical Durability by Annealing of SPEEK Membrane for Polymer Electrolyte Fuel Cells (고분자 전해질 연료전지용 SPEEK 막의 어닐링에 의한 화학적 내구성 향상)

  • MI-HWA LEE;DONGGEUN YOO;HYE-RI LEE;IL-CHAI NA;KWONPIL PARK
    • 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.

A Study on Irreversible Degradation through OCV Reduction and Recovery Behavior in the Electrochemical Degradation Process of PEMFC Polymer Membrane (PEMFC 고분자 막의 전기화학적 열화과정에서 OCV 감소 및 회복 거동을 통한 비가역적 열화 연구)

  • Yoo, Donggeun;Park, Kwon-Pil
    • 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.

Comparison of Membrane Degradation of PEMFC by Fenton Reaction and OCV Holding (Fenton 반응과 OCV Holding에 의한 PEMFC 고분자 전해질 막의 열화비교)

  • Oh, Sohyung;Kwag, Ahhyun;Lee, Daewoong;Lee, Mooseok;Lee, Donghoon;Park, Kwon-Pil
    • 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.