• 한국안전학회지
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• 제37권6호
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• pp.18-24
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• 2022

Hydrogen is a clean fuel and is used in many applications in power systems such as fuel cells. It has unique properties such as wide flammability, high burning velocity, and difficulty to liquefy, which lead to critical safety issues. Fire and explosion are the most frequently occurring accidents and one of the major reasons is autoignition. In the ignition process, the chemistry of hydrogen combustion depends mainly on radical pools, and the temperature at which chain-branching and terminating rates are equal is called the crossover temperature. This study addresses the homogeneous autoignition of diluted hydrogen-air mixtures to investigate the effects of dilution on the crossover temperature to prevent explosions in the future. The new criterion for crossover temperature is introduced by only hydrogen radicals to adjust more simply. The detailed calculations indicate that the crossover temperatures are low at high dilutions of carbon dioxide and nitrogen because the concentrations of active radicals are reduced when an inert gas is added. This result is expected to contribute to hydrogen safety and realize a hydrogen society in the future.

• Korean Journal of Chemical Engineering
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• 제35권11호
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• pp.2290-2295
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• 2018

An acceleration stress test (AST) was performed to evaluate the durability of a polymer membrane in a polymer electrolyte membrane fuel cell (PEMFC) for 500 hours. Previous studies have shown that hydrogen crossover measured by linear sweep voltammetry (LSV) increases when the polymer membrane deteriorates in the AST process. On the other hand, hydrogen crossover of the membrane often decreases in the early stages of the AST test. To investigate the cause of this phenomenon, we analyzed the MEA operated for 50 hours using the AST method (OCV, RH 30% and $90^{\circ}C$). Cyclic voltammetry and transmission electron showed that the electrochemical surface area (ECSA) decreased due to the growth of electrode catalyst particles and that the hydrogen crossover current density measured by LSV could be reduced. Fourier transform infrared spectroscopy and thermogravimetric/differential thermal analysis showed that -S-O-S- crosslinking occurred in the polymer after the 50 hour AST. Gas chromatography showed that the hydrogen permeability was decreased by -S-O-S- crosslinking. The reduction of the hydrogen crossover current density measured by LSV in the early stages of AST could be caused by both reduction of the electrochemical surface area of the electrode catalyst and -S-O-S- crosslinking.

• 대한기계학회논문집B
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• 제33권3호
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• pp.207-214
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• 2009

Crossover of nitrogen from cathode to anode is inevitable in typical membranes used in PEM fuel cells. This crossovered nitrogen normally accumulates in the hydrogen recirculation system at anode side channels. Excessive buildup of nitrogen in the anode side lowers the relative hydrogen concentration and finally affects the performance of fuel cell stack. So it is very important to analysis the nitrogen gas crossover at various operating conditions. In this study, characterization of nitrogen gas crossover in PEM fuel cell stack was investigated. The mass spectroscopy (MS) has been applied to measure the amount of the crossovered nitrogen gas at the anode exit. Results show that nitrogen gas crossover rate was affected by current density, anode and cathode stoichiometric ratio and operating pressure. Current density, anode stoichiometric ratio and anode operating pressure do not affect nitrogen crossover rate but anode exit concentration of nitrogen. Cathode pressure and stoichiometric ratio largely affect the nitrogen crossover rate.

• Korean Chemical Engineering Research
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• 제56권2호
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• pp.151-155
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• 2018

고분자전해질 연료전지(PEMFC)의 고분자막 열화정도는 주로 수소투과전류밀도로 평가한다. 수소투과전류밀도는 선형주사전압전류측정법(Linear Sweep Voltammetry, LSV)으로 측정하는데 DOE프로토콜과 NEDO프로토콜이 분석방법에 차이가 있다. 본 연구에서는 PEMFC 구동 및 가속 열화 시험 과정에서 두 프로토콜을 적용해 수소투과 전류밀도를 비교하였다. DOE 방법에 의한 LSV 방법에서는 주사속도(scan rate) 변화가 수소투과 전류밀도에 영향을 주지만 NEDO 방법에서는 주사속도가 수소투과전류밀도에 영향을 주지 않았다. 고분자막 가습/건조 15,000사이클 평가과정에서 DOE 방법은 막의 열화를 민감하게 측정하였으나 NEDO방법은 DOE방법에 비해 막의 열화가 덜 민감하게 나타났다.

• Korean Chemical Engineering Research
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• 제53권4호
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• pp.412-416
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• 2015

고분자 막 성능 평가 및 내구성 평가에 이용하기 위해 고분자전해질 연료전지(PEMFC) 구동 중에 수소 크로스오버 측정이 필요하다. 수소 크로스오버 측정 시에 불활성 기체 대신에 공기를 cathode에 공급하면서 기체 크로마토그래프로 수소 농도를 cathode 출구에서 분석하였다. PEMFC 구동 중 고분자 막을 통과한 수소는 cathode에서 산소와 반응해 불활성 가스를 공급할 때에 비해 수소 농도가 감소하였다. cathode 공기 공급 유량이 증가하면 수소 농도가 감소했고, 셀의 온도와 습도, 압력이 증가하면 cathode의 수소 농도는 증가했다. 일반적인 PEMFC 구동 조건에서 $120mA/cm^2$ 전류밀도에서 수소농도는 약 5.0 ppm이었다.

• Korean Chemical Engineering Research
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• 제52권4호
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• pp.425-429
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• 2014

최근까지 대부분의 PEMFC MEA(Membrnae and Electrode Assembly) 열화 연구는 전극과 전해질 막 각각 분리되어 연구되었다. 그런데 실제 PEMFC 운전조건에서는 전극과 전해질 막은 동시에 열화된다. 동시열화과정에서 전극열화와 전해질 막 열화는 상호 작용한다. 전해질 막의 열화정도를 측정하는데 수소투과도가 많이 사용되고 있다. 그런데 동시 열화가 발생했을 때 선형 쓸음 전기량 측정법(Linear Sweep Voltammetry, LSV)에 의해 수소투과도를 측정하면 전극열화가 수소투과전류를 감소시키는데, LSV 방법이 전극 촉매의 활성 면적에 의존하기 때문이다. 본 연구에서는 전극과 막 동시 열화과정에서 기체 크로마토그래프에 의한 PEMFC 전해질막의 수소투과도를 측정하였다. 기체 크로마토그래프 측정 방법은 전극 상태와 무관하기 때문에 전극과 막 동시 열화 과정에서 수소투과도가 전극 열화 영향을 받지 않음을 확인하였다.

• Korean Chemical Engineering Research
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• 제51권3호
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• pp.325-329
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• 2013

실제 고분자 전해질 연료전지(PEMFC) 운전조건에서는 전극과 전해질 막은 동시에 열화된다. 그런데 고분자전해질 연료전지의 전극 열화와 전해질 열화의 상호 작용에 대해 연구되지 않았다. 본 연구에서는 전해질 막 열화가 전극 열화에 미치는 영향에 대해 연구하였다. 전해질 막 열화 후 전극을 열화시켜 전해질 막 열화없이 전극을 열화시켰을 때와 비교하였다. 열화전후의 I-V 성능, 수소투과전류, 순환 전압측정(CV), 임피던스, TEM 등을 측정하였다. 전해질 막열화에 의해 수소투과도가 증가하고, 이에 따라 백금 입자 성장속도가 감소함으로써 전극 열화속도가 감소함을 보였다.

• 대한기계학회:학술대회논문집
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• 대한기계학회 2008년도 추계학술대회B
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• pp.2227-2230
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• 2008

Crossover of nitrogen from cathode to anode is inevitable in typical membranes used in PEM fuel cells. This crossovered nitrogen accumulates in anode recirculation system and excessive buildup of nitrogen in the recirculating anode gas lowers the hydrogen concentration and finally affects the performance of fuel cell stacks. In this study, characterization of nitrogen gas crossover was investigated in PEM fuel cell stacks. The mass spectroscopy (MS) has been applied to measure the amount of the crossovered nitrogen at the exit of anode. Results show that anode and cathode stoichiometric number ($SR_c$) have a big effect of nitrogen crossover.

• 한국수소및신에너지학회논문집
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• 제22권3호
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• pp.292-298
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• 2011

This study examines the effects of the ambient temperature (AT), methanol feeding temperature (MFT), methanol concentration (MC) and methanol flow rate (MFR) on the performance and cell temperature (CT) of a 5-stacked direct methanol fuel cell (DMFC). The AT, MFT, MC, and MFR are varied from $-10^{\circ}C$ to $+40^{\circ}C$, $50^{\circ}C$ to $90^{\circ}C$, 0.5M to 3.0M and 11.7 mL $min^{-1}$ to 46.8 mL $min^{-1}$, respectively. The performance of the DMFC under various operating conditions is analyzed from the I-V polarization curve, and the methanol crossover is estimated by gas chromatography (GC). The performance of the DMFC improves significantly with increasing AT. The open circuit voltage (OCV) decreases with increasing MC due to the enhanced likelihood of methanol crossover. The cell performance is improved significantly when the MFR is increased from 11.7 mL $min^{-1}$ to 28.08 mL $min^{-1}$. The change in cell performance is marginal with further increases in MFR. The CT increases significantly with increasing AT. The effect of the MFT and MFR is moderate, and the effect of MC is marginal on the CT of the DMFC.

• 한국수소및신에너지학회논문집
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• 제19권6호
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• pp.467-473
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• 2008

This study is to investigate the influence of catalyst loading quantity on the direct methanol fuel cell (DMFC) performance. In this paper, Pt-Ru and Pt-black loading as the catalyst were varied from 1 to $4mg/cm^2$ at the anode and cathode, respectively. The experiment was conducted with single fuel cell consisted of $5cm^2$ effective electrode area, serpentine type flow pattern and Nafion 117 membrane. Also, AC impedance and methanol crossover current were measured to investigate the performance loss precisely. As a result, the performance of fuel cell was significantly increased with the increase of cathode catalyst loading. However, the performance did not increase further above a certain Pt-Ru catalyst loading as the increase of anode catalyst loading.