• Title/Summary/Keyword: Pt dissolution

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Study on a Long Term Deactivation of Electro-catalysts in PEMFC for Automobile (자동차용 PEMFC 전극 촉매의 열화 원인에 대한 연구)

  • Chung, Jong-Shik;Chung, Chul-Goo;Kim, Lim;Sung, Yong-Wook
    • 한국신재생에너지학회:학술대회논문집
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    • 2006.06a
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    • pp.63-66
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    • 2006
  • A long term deactivation study was carried out with commercial MEA provided by Hyundai Motor Co. The deactivation phenomena were observed only at high voltage region where there is no diffusion-limited reaction. A rapid deactivation was observed up to 40h owing to the sintering of Pt particles. This was followed a gradual increase in the activity up to 300 h, which is probably caused by improvement in the electrode properties in the presence of current during the reaction. After 300 h, monotonic decrease in the activity was observed owing to dissolution of Pt particles especially in the cathode. The presence oxygen is the cause of oxidation and dissolution of Pt. The dissolution rate can be somewhat retarded by generation of current, which reduces Pt ion back to Pt in the cathode.

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A Study of the Electrode Catalyst Migration and Aging Mechanism of PEMFC (고분자연료전지 내 촉매 이동 및 노화메커니즘에 관한 연구)

  • Lee, Yoon-Hee;Lee, Ki-Suk;Yun, Jong-Jin;Byun, Jung-Yeon
    • 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.

Carbon Corrosion at Pt/C Interface in Proton Exchange Membrane Fuel Cell Environment

  • Choi, Min-Ho;Beom, Won-Jin;Park, Chan-Jin
    • Corrosion Science and Technology
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    • v.9 no.6
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    • pp.281-288
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    • 2010
  • This study examined the carbon corrosion at Pt/C interface in proton exchange membrane fuel cell environment. The Pt nano particles were electrodeposited on carbon substrate, and then the corrosion behavior of the carbon electrode was examined. The carbon electrodes with Pt nano electrodeposits exhibited the higher oxidation rate and lower oxidation overpotential compared with that of the electrode without Pt. This phenomenon was more active at $75^{\circ}C$ than $25^{\circ}C$. In addition, the current transients and the corresponding power spectral density (PSD) of the carbon electrodes with Pt nano electrodeposits were much higher than those of the electrode without Pt. The carbon corrosion at Pt/C interface was highly accelerated by Pt nano electrodeposits. Furthermore, the polarization and power density curves of PEMFC showed degradation in the performance due to a deterioration of cathode catalyst material and Pt dissolution.

Hybrid PtCo Alloy Nanocatalysts Encapsulated by Porous Carbon Layers for Oxygen Reduction Reactions (다공성 탄소층이 코팅된 하이브리드 표면 구조를 갖는 산소 환원 반응용 PtCo 합금 나노 촉매)

  • Jang, Jeonghee;Sharma, Monika;Sung, Hukwang;Kim, Sunpyo;Jung, Namgee
    • Korean Journal of Materials Research
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    • v.28 no.11
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    • pp.646-652
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    • 2018
  • During a long-term operation of polymer electrolyte membrane fuel cells(PEMFCs), the fuel cell performance may degrade due to severe agglomeration and dissolution of metal nanoparticles in the cathode. To enhance the electrochemical durability of metal catalysts and to prevent the particle agglomeration in PEMFC operation, this paper proposes a hybrid catalyst structure composed of PtCo alloy nanoparticles encapsulated by porous carbon layers. In the hybrid catalyst structure, the dissolution and migration of PtCo nanoparticles can be effectively prevented by protective carbon shells. In addition, $O_2$ can properly penetrate the porous carbon layers and react on the active Pt surface, which ensures high catalytic activity for the oxygen reduction reaction. Although the hybrid catalyst has a much smaller active surface area due to the carbon encapsulation compared to a commercial Pt catalyst without a carbon layer, it has a much higher specific activity and significantly improved durability than the Pt catalyst. Therefore, it is expected that the designed hybrid catalyst concept will provide an interesting strategy for development of high-performance fuel cell catalysts.

Studies on Suppositories of $Phenytoin-{\beta}-Cyclodextrin$ Inclusion Complexes (페니토인-${\beta}$-시클로덱스트린 포접 복합체의 좌제에 관한 연구)

  • Cha, Jae-Ho;Han, Kun
    • Journal of Pharmaceutical Investigation
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    • v.18 no.1
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    • pp.15-21
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    • 1988
  • An inclusion complex of phenytoin (PT) with ${\beta}-cyclodextrin\;({\beta}-CyD)$ in molar ratio of 1 : 1 was prepared, and the interaction between host and guest molecules was confirmed by infrared spectrometry, differential scanning calorimetry and X-ray diffractometry. Suppositories were prepared by the fusion method. PT and $PT-{\beta}-CyD$ complex were added to PEG 1540 and Witepsol H-15 under the vigorous stirring at $40^{\circ}C$. Content uniformity was tested for different formulations of the PT suppositories. The release rates were dependent on the K.P. V dissolution apparatus and the dialyzing tubing method. Then, the release rates were increased in the following order: $PT-{\beta}-CyD$ complex in PEG 1540>PT in PEG 1540>$PT-{\beta}-CyD$ complex in Witepsol H-15>PT in Witepsol H-15. The area under the curve and maximum blood concentration after rectal administration were increased in the following order: $PT-{\beta}-CyD$ complex in PEG 1540>PT in PEG 1540>$PT-{\beta}-CyD$ complex in Witepsol H-15>PT in Witepsol-15.

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Synthesis and Durability of Carbon-Supported Catalysts for PEMFC (내구성 향상을 위한 연료전지 촉매 개발)

  • YI, MI HYE;CHOI, JIN SUNG;RHO, BUMWOOK
    • Transactions of the Korean hydrogen and new energy society
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    • v.26 no.4
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    • pp.318-323
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    • 2015
  • For commercialization of fuel cell electric vehicles, one of the key objectives is to improve durability of MEA and electrocatalysts. Regarding electrocatalysts, the major issue is to reduce carbon corrosion and dissolution of Pt caused by harsh conditions, for example, SU/SD (Start-up/Shut-down). In this research, OER (Oxygen Evolution Reaction) catalyst has been developed improvement of durability. A modified polyol process is developed by controlling the pH of the solvent to synthesize the PtIr nanocatalysts on carbon supports. Each performance of the MEAs applying PtIr and Pt are equivalent because PtIrnanocatalysts have both ORR and OER activity. Breadboard test for catalyst durability in harsh conditions and high potentialsis found that the MEA applying PtIrnanocatalysts durability is improved more than the MEA applying Pt nanocatalysts.

Effect of Pt-Co/C Cathode Catalyst on Electrochemical Durability of Membrane in PEMFC (PEMFC에서 Pt-Co/C Cathode 촉매가 고분자막의 전기화학적 내구성에 미치는 영향)

  • Sohyeong Oh;Dong Geun Yoo;Myoung Hwan Kim;Ji Young Park;Kwonpil Park
    • 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.

Comparison of Catalyst Support Degradation of PEMFC Electrocatalysts Pt/C and PtCo/C (PEMFC 전극촉매 Pt/C와 PtCo/C의 촉매 지지체 열화비교)

  • Sohyeong Oh;Yoohan Han;Minchul Chung;Donggeun Yoo;Kwonpil Park
    • Korean Chemical Engineering Research
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    • v.61 no.3
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    • pp.341-347
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    • 2023
  • In PEMFC, PtCo/C alloy catalysts are widely used because of good performance and durability. However, few studies have been reported on the durability of carbon supports of PtCo/C evaluated at high voltages (1.0~1.5 V). In this study, the durability of PtCo/C catalysts and Pt/C catalysts were compared after applying the accelerated degradation protocol of catalyst support. After repeating the 1.0↔1.5V voltage change cycles, the mass activity, electrochemical surface area (ECSA), electric double layer capacitance (DLC), Pt dissolution and the particle growth were analyzed. After 2,000 cycles of voltage change, the current density per catalyst mass at 0.9V decreased by more than 1.5 times compared to the Pt/C catalyst. This result was because the degradation rate of the carbon support of the PtCo/C catalyst was higher than that of the Pt/C catalyst. The Pt/C catalyst showed more than 1.5 times higher ECSA reduction than the PtCo/C catalyst, but the corrosion of the carbon support of the Pt/C catalyst was small, resulting in a small decrease in I-V performance. In order to improve the high voltage durability of the PtCo/C catalyst, it was shown that improving the durability of the carbon support is essential.

Anode processes on Pt and ceramic anodes in chloride and oxide-chloride melts

  • Mullabaev, A.R.;Kovrov, V.A.;Kholkina, A.S.;Zaikov, Yu.P.
    • Nuclear Engineering and Technology
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    • v.54 no.3
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    • pp.965-974
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    • 2022
  • Platinum anodes are widely used for metal oxides reduction in LiCl-Li2O, however high-cost and low-corrosion resistance hinder their implementation. NiO-Li2O ceramics is an alternative corrosion resistant anode material. Anode processes on platinum and NiO-Li2O ceramics were studied in (80 mol.%) LiCl-(20mol.%)KCl and (80 mol.%)LiCl-(20 mol.%)KCl-Li2O melts by cyclic voltammetry, potentiostatic and galvanostatic electrolysis. Experiments performed in the LiCl-KCl melt without Li2O illustrate that a Pt anode dissolution causes the Pt2+ ions formation at 3.14 V and 550℃ and at 3.04 V and 650℃. A two-stage Pt oxidation was observed in the melts with the Li2O at 2.40 ÷ 2.43 V, which resulted in the Li2PtO3 formation. Oxygen current efficiency of the Pt anode at 2.8 V and 650℃ reached about 96%. The anode process on the NiO-Li2O electrode in the LiCl-KCl melt without Li2O proceeds at the potentials more positive than 3.1 V and results in the electrochemical decomposition of ceramic electrode to NiO and O2. Oxygen current efficiency on NiO-Li2O is close to 100%. The NiO-Li2O ceramic anode demonstrated good electrochemical characteristics during the galvanostatic electrolysis at 0.25 A/cm2 for 35 h and may be successfully used for pyrochemical treating of spent nuclear fuel.

Performance Enhancement by Adaptation of Long Term Chronoamperometry in Direct Formic Acid Fuel Cell using Palladium Anode Catalyst

  • Kwon, Yong-Chai;Baik, S.M.;Han, Jong-Hee;Kim, Jin-Soo
    • Bulletin of the Korean Chemical Society
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    • v.33 no.8
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    • pp.2539-2545
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    • 2012
  • In the present study, we suggest a new way to reactivate performance of direct formic acid fuel cell (DFAFC) and explain its mechanism by employing electrochemical analyses like chronoamperometry (CA) and cyclic voltammogram (CV). For the evaluation of DFAFC performance, palladium (Pd) and platinum (Pt) are used as anode and cathode catalysts, respectively, and are applied to a Nafion membrane by catalyst-coated membrane spraying. After long DFAFC operation performed at 0.2 and 0.4 V and then CV test, DFAFC performance is better than its initial performance. It is attributed to dissolution of anode Pd into $Pd^{2+}$. By characterizations like TEM, Z-potential, CV and electrochemical impedance spectroscopy, it is evaluated that such dissolved $Pd^{2+}$ ions lead to (1) increase in the electrochemically active surface by reduction in Pd particle size and its improved redistribution and (2) increment in the total oxidation charge by fast reaction rate of the Pd dissolution reaction.