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PEMFC에서 Pt-Co/C Cathode 촉매가 고분자막의 전기화학적 내구성에 미치는 영향
오소형,유동근,김명환,박지용,박권필 한국화학공학회 2023 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.61 No.2
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.
박권필,오소형,유동근,김명환,박지용,최영진 한국화학공학회 2023 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.61 No.4
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.
오소형,곽아현,오성준,이대웅,나일채,박권필 한국화학공학회 2020 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.58 No.1
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. PEMFC 고분자막의 내구성을 향상시키기 위해서 Radical 제거제가 사용되고 있다. 본 연구에서는 라디칼 제거제로서해조류에서 추출한 후코이단이 고분자막의 전기화학적 열화를 방지하는지 Fenton 실험과 가속내구 평가방법(OCV Holding) 실험을 통해 검토하였다. 후코이단은 항산화 효과가 있어 과산화수소와 산소 라디칼로부터 고분자막을 보호해 열화속도를 1/10로 감소시켰다. 후코이단이 라디칼 제거제로 사용되는 MnO2보다 효과적임을 보였다. PEMFC셀에서OCV Holding 실험한 결과, 후코이단이 고분자막의 수소투과도를 12% 감소시켰고, 성능은 라디칼 제거제가 없을 때보다 29.1% 감소시켜 PEMFC 셀에서도 라디칼 제거제의 역할을 함을 확인하였다. 그리고 후코이단을 Anode쪽보다Cathode 쪽 전극 이오노머에 넣은 것이 더 효과적임을 확인하였다.
김태희,이정훈,이호,임태원,박권필 한국수소및신에너지학회 2007 한국수소 및 신에너지학회논문집 Vol.18 No.2
During PEMFC operation, low current and low humidity conditions accelerate the degradation of perfluorosulfonic acid membrane. But, 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) in effluent water were measured during cell operation under low current densities 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 radical formation on the Pt catalyst and the low current condition accelerates the to form radical attacking the polymer membrane.
Degradation of proton exchange membrane by Pt dissolved/deposited in fuel cells
Taehee Kim,Ho Lee,심우종,Jonghyun Lee,Saehoon Kim,Taewon Lim,박권필 한국화학공학회 2009 Korean Journal of Chemical Engineering Vol.26 No.5
An accelerated single cell test and single electrode cell test were carried out to investigate membrane degradation by Pt dissolved/deposited on the membrane. For a cell operating under accelerated conditions (OCV, 90℃, anode RH 0%, cathode O2 supply), MEA analyses revealed that Pt particles were deposited in the membrane at the anode side, with a decrease in F, O, and C content near the anode side of the membrane. Dissolved Pt from the cathode showed that Pt existed mainly in the form of Pt2+ ionic species. Oxygen and hydrogen helped Pt dissolution from the cathode and Pt deposition in the membrane, respectively. Radical formation on deposited Pt in the membrane was detected by electron spin resonance (ESR). Fluoride emission rate (FER, an indicator of membrane degradation rate) increased with an increase in the amount of Pt in the membrane.