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양성자 교환막 연료전지의 사형 유로 깊이에 따른 NaCl 수용액의 영향

Effects of NaCl Solution on Proton Exchange Membrane Fuel Cell with Serpentine Flow Channel of Different Depths

Journal of the Korean Society for Precision Engineering 2025;42(5):399-403.
Published online: May 1, 2025

1 단국대학교 기계공학과

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#E-mail: guyoungcho@dankook.ac.kr, TEL: +82-31-8005-3520
E-mail: gipark@seas.upenn.edu, TEL: +1-215-898-5596
• Received: March 13, 2025   • Accepted: April 29, 2025

Copyright © The Korean Society for Precision Engineering

This is an Open-Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://creativecommons.org/licenses/by-nc/3.0) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.

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  • Degradation of proton exchange membrane fuel cells (PEMFCs) can be accelerated by impurities in the air. In maritime environments in particular, sodium chloride (NaCl) can reduce the performance of membrane electrode assembly (MEA) in PEMFCs. In this context, we experimentally analyzed effect of flow channel depth on PEMFCs humidified with a NaCl solution at the cathode side. The analysis was conducted in serpentine flow channels with different depths of 0.4, 0.8, and 1.6 mm. The initial performance of unit cells was compared to their performance after applying a constant current for 10 hours. Results showed that the degradation rate correlated positively with the flow-channel depth. Channel depths of 0.4 and 1.6 mm resulted in 2.4% and 7.3% decreases in the maximum power density, respectively. For the 1.6 mm channel depth, the activation loss after 10 hours was larger than the initial loss.
세계적으로 탄소배출에 대한 규제가 강화되면서 신재생에너지에 대한 연구가 활발히 이루어지고 있다. 수소 에너지를 이용하는 연료전지는 수소와 산소의 전기화학반응을 이용하여 전기를 생산하는 장치이다. 연료전지는 전해질의 특성에 따라 여러 종류로 나뉘어져 있으며, 대표적으로 양성자 교환막 연료전지(Proton Exchange Membrane Fuel Cell, PEMFC)와 고체 산화물연료전지(Solid Oxide Fuel Cell, SOFC)가 있다. 이 중 PEMFC는 다른 연료전지에 비해 높은 성능, 100oC 이하의 저온 작동, 높은 확장성과 빠른 시동 및 정지 등의 장점을 가지고 있다[1]. 이러한 장점들은 특히 수송 수단에 적합하여 자동차, 선박, 항공 등 다양한 분야에서 활용되고 있다[2].
하지만 PEMFC는 촉매인 백금의 특성과 낮은 작동온도로 인해 불순물에 매우 취약하다[3,4]. 특히 해양환경의 공기에 포함된 염화나트륨(NaCl)이 막전극복합체(Membrane Electrode Assembly, MEA)의 열화를 가속시키는 것으로 알려져 있다. Okada et al.은 나트륨 이온(Na+)이 전해질막 속의 수소 이온을 대체하여 PEMFC의 성능을 저하시킨다고 보고하였다[5]. Yadav et al.은 염화 이온(Cl-)이 백금 촉매의 용해를 유도한다는 것을 실험적으로 검증하였다[6]. Li et al.은 장시간의 실험을 통하여 염화이온이 PEMFC의 성능과 내구성을 악화시킨다는 것을 보였다[7,8]. 그 외에도 공기극에 공급되는 NaCl의 부정적인 영향에 대한 연구가 다수 진행되었다[9-14].
한편, 유로의 형상은 PEMFC의 성능과 물질 전달에 큰 영향을 끼친다. NaCl은 유로를 통하여 반응물과 함께 MEA에 공급되기 때문에, NaCl의 영향을 분석할 때 유로의 형상도 함께 고려해야 할 필요가 있다. Yoo et al.은 평행 유로와 사형 유로에 대한 NaCl 수용액 가습의 영향을 조사하였다[15]. 해당 연구에 따르면 사형 유로는 평행 유로에 비해 NaCl에 의한 열화에 취약한 반면 회생에는 강점을 보이는 것으로 나타났다.
본 연구에서는 NaCl 수용액으로 가습된 공기극에서 사형 유로의 깊이가 미치는 영향을 분석하기 위하여 10시간의 정전류 실험을 수행하였다. 단위 셀의 초기 성능과 정전류 실험을 한 이후의 성능을 서로 비교하였다. 3개의 서로 다른 깊이를 가진 유로를 사용하였으며, 각 유로에서 보인 경향을 서로 비교하고 분석하였다.
실험에 사용된 연료전지 단위 셀(Unit Cell)의 활성화 면적은 2.3 × 2.2 cm2이다. MEA는 CNL Energy사에서 제작된 상용 제품을 사용하였다. 기체확산층은 연료극과 공기극에 모두 SGL (Germany)사의 39 BB 모델을 이용하였다. 분리판은 사형 유로가 새겨진 흑연 재질의 분리판을 사용하였다.
Fig. 1은 실험에 사용된 시스템의 구조이다. 단위 셀의 전기화학적 특성은 BioLogic (France)사의 SP-150 (Potentiostat)과 VMP3B-10 (External Booster)을 사용하여 측정하였다. 공기극에는 탈이온수(Deionized Water, DI Water)가 담긴 버블러와 NaCl 10 wt% 수용액이 담긴 버블러를 3방밸브(3-way Valve)를 이용하여 연결하였으며, 500 sccm의 공기를 공급하였다. 연료극에는 100 sccm의 수소를 건조한 상태로 공급하였다. 모든 실험은 상온 및 상압 조건에서 진행되었다.
Fig. 1

Schematic of NaCl contamination setup

KSPE_2025_v42n5_399_f001.jpg
본 연구에서 수행한 네 번의 실험을 Table 1에 나열하였다. 먼저 동일한 유로 깊이(0.8 mm)를 가진 단위 셀에 DI Water와 NaCl 수용액을 각각 가습시킨 실험결과를 비교하여 NaCl 오염의 영향을 확인하였다. 이후 유로 깊이가 더 낮은 경우(0.4 mm)와 더 깊은 경우(1.6 mm)에 대해 실험을 진행하고 결과를 비교하였다. 모든 Case에서 유로와 격벽(Rib)의 폭은 각각 1.0과 1.1 mm로 일정하다.
Table 1

Humidification medium and channel parameters of each case

Table 1
Case Humidification medium Design parameters of channel
Depth [mm] Width [mm]
1 DI water 0.8 1.0
2 NaCl solution 0.8
3 NaCl solution 0.4
4 NaCl solution 1.6
활성화 과정에서의 공기극 가습은 모두 DI Water로 진행하였다. 단위 셀의 성능을 비교 및 분석하기 위해 전류밀도-전압곡선(IV Curve) 및 전기화학 임피던스 분광법(Electrochemical Impedance Spectroscopy, EIS) 측정을 수행하였다. 초기 성능을 측정한 후, 장기 내구성 평가를 위하여 일정한 크기의 전류를 단위 셀에 10시간 동안 지속적으로 인가하며 전압을 측정하였다. 이때 전류의 크기는 각 Case 별로 초기에 측정한 IV 곡선에서 0.6 V에 대응되는 값을 적용하였다. 10시간의 전압 측정 이후, 다시 IV 곡선과 EIS 측정을 진행하고 초기 성능과 비교하였다.
Fig. 2(a)는 단위 셀에 대한 IV 곡선의 변화를 나타낸다. 탈이온수로 가습시킨 경우, 초기 성능과 10시간 이후의 성능 사이에 차이가 거의 없는 것을 볼 수 있다. 하지만 NaCl 수용액으로 가습시킨 경우, 10시간 이후의 성능이 초기 성능에 비해 낮아졌다. 특히 전류밀도가 높아지면서 성능 감소의 폭이 커짐을 볼 수 있다. 이는 성능의 감소가 물질전달과 관련이 있음을 나타낸다. 또한 유로의 깊이가 0.4 mm인 경우 성능 감소의 폭이 비교적 작았고, 반대로 깊이가 1.6 mm인 경우 성능이 더욱 감소한 것을 알 수 있다. Figs. 2(b)와 2(c)는 각각 전류밀도에 따른 전력밀도 곡선과 최대 전력밀도를 나타낸다. 탈이온수를 사용하였을 때는 최대 전력밀도가 471.9에서 468.8 mW/cm2로 0.7% 감소하였다. 같은 유로에서 NaCl 수용액으로 가습한 경우 최대 전력밀도는 469.8에서 446.2 mW/cm2로 5.0% 감소하였다. 이는 NaCl 수용액으로 인해 PEMFC 성능이 낮아졌다는 것을 나타낸다. 유로의 깊이가 0.4 mm인 경우 469.4에서 458.2 mW/cm2로 2.4%만큼, 깊이가 1.6 mm인 경우 459.2에서 425.9 mW/cm2로 7.3%만큼 감소하였다.
Fig. 2

Changes in electrochemical characteristics for each case

KSPE_2025_v42n5_399_f002.jpg
앞서 언급하였듯이 유로의 깊이에 따른 열화율을 비교하기 위하여 10시간 동안 단위 셀에 일정한 크기의 전류를 가하였다. 일반적으로 PEMFC는 정전류법(Galvanostatic Techniques)으로 작동하기 때문에[16-17] IV 곡선의 특정 전압(0.6 V)에서 측정된 전류를 각각 인가하였다. 시간에 따른 전압의 변화를 Fig. 3에 나타내었다. 모든 경우에서 전압은 초기에 약 0.57 V가 측정되었으며, 시간이 지날수록 전압이 감소하였다. 유로의 깊이가 0.8 mm일 때 탈이온수로 가습시킨 경우의 평균 열화율은 3.4 mV/hr, NaCl 수용액으로 가습시킨 경우는 4.7 mV/hr으로 나타났다. 또한 0.4 mm 깊이에서 평균 열화율은 4.1 mV/hr, 1.6 mm 깊이일 때 6.6 mV/hr으로 나타났다. 이는 유로의 깊이가 얕을수록 장기간 작동에서 유리하다는 것을 의미한다.
Fig. 3

Voltage changes at constant current as a function of time in 10 hours. The value of the applied current was determined by the current measured at 0.6 V in the initial IV curve

KSPE_2025_v42n5_399_f003.jpg
Fig. 4에 NaCl 수용액으로 가습시킨 실험의 EIS 측정 결과를 Nyquist 선도로 나타내었다. EIS의 등가회로 모델은 Dhirde가 제안한 모델을 사용하였다[18]. 해당 그래프에서 고주파수 영역에 위치한 X축 절편은 오믹 저항을 의미하며, 그래프가 나타내는 첫 번째 반원의 크기는 활성화 저항을 의미한다. 두 번째 반원의 크기는 물질전달 저항을 나타내지만, 본 실험에서는 물질전달이 활발한 사형 유로로 구성된 소면적 셀(5.06 cm2)을 이용하였으므로 해당 그래프에서는 거의 나타나지 않았다. 2개의 그래프를 살펴보면 유로의 깊이가 얕을수록 오믹 저항이 커지고 활성화 저항이 작아지는 것을 알 수 있다. 이는 동일한 유량의 반응물이 공급될 경우 유로의 깊이가 얕을수록 유속이 증가하는 것과 연관이 있다. 유속이 증가할수록 대류에 의한 물의 제거가 활발해지며, 이는 전해질막의 수분 함량 감소를 야기하여 오믹 저항이 증가한다. 동시에 압력이 높아지면서 반응물의 농도가 증가하여 활성화 저항은 감소하게 된다[19].
Fig. 4

EIS measurement @ 0.5 V for each case humidified with NaCl solution

KSPE_2025_v42n5_399_f004.jpg
Table 2에 유로 깊이에 따른 PEMFC의 성능 저하율 및 활성화저항 증가율을 정리하였다. 초기의 저항 크기와 10시간 후의 저항 크기를 비교할 경우 오믹 저항은 큰 변화를 나타내지 않았다. 유로 깊이가 0.8 mm인 경우 활성화 저항은 323.5에서 339.0 mΩ·cm2으로 4.8% 증가하였고, 0.4 mm인 경우 281.2에서 285.1 mΩ·cm2로 1.4% 증가하였다. 반면에 유로 깊이가 1.6 mm인 경우, 활성화 저항은 361.6에서 384.4 mΩ·cm2로 6.3% 증가하였다. 이는 유로의 깊이에 따른 물질전달이 활성화 저항에 영향을 끼친다는 것을 의미한다. 앞서 언급한 선행연구에 의하면 NaCl의 염화 이온이 촉매층 내부에 흡착된 후 백금의 용해를 유도하여 PEMFC의 성능을 저하시킨다[6]. 유로의 깊이가 얕을수록 활성화 저항이 감소하는 것은 활발한 대류 현상이 촉매층 내의 NaCl을 효과적으로 제거한 결과임을 유추할 수 있다.
Table 2

Performance changes of NaCl solution cases with different channel depths

Table 2
Channel depth [mm] 0.4 0.8 1.6
Degradation rate
@ Max. power [%]
2.4 5.0 7.3
Increase rate of activation
loss [%]
1.4 4.8 6.3
본 연구에서는 사형 유로의 깊이에 따라 NaCl 수용액이 PEMFC 단위 셀의 열화에 미치는 영향을 비교 및 분석하였다. 이를 위해 10시간 동안 정전류 실험을 진행하였으며 그 이후의 셀 성능을 초기 성능과 비교하였다.
유로의 깊이가 0.4 mm인 경우 최대 전력밀도가 10시간 이후에 2.4%만큼 감소한 반면, 유로의 깊이가 1.6 mm인 경우 최대 전력밀도가 7.3%만큼 감소하였다. EIS 그래프를 통하여 0.4 mm 깊이의 경우 활성화 저항이 1.4%만큼 증가하는 동안 1.6 mm 깊이에서 활성화 저항이 6.3%만큼 증가한 것을 확인하였다.
이를 통해 사형 유로의 깊이가 얕을수록 활발해진 대류 현상이 촉매층에 공급된 NaCl 입자를 효과적으로 제거하여 장기간 작동에 유리하다는 것을 알 수 있다. 하지만 PEMFC의 압력강하가 높아질수록 기생손실 또한 증가하기 때문에 적절한 깊이와 형상을 선정하는 것이 중요하다.
이 논문은 정부(과학기술정보통신부)의 재원으로 한국연구재단의 지원을 받아 수행된 연구임(No. RS-2023-00213741). 본연구는 산업통상자원부와 한국산업기술진흥원이 지원한 산업혁신인재양성지원사업(해외연계)(No. RS-2024-00435841)으로 수행된 연구결과임. 본 논문은 경기도 기술개발사업의 연구개발지원(No. H2409002)에 의해 수행되었습니다.
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Dong Kun Song
KSPE_2025_v42n5_399_bf001.jpg
Ph.D. candidate in the Department of Mechanical Engineering, Dankook University. His research interests are fuel cells and fluid dynamics.
Ho Jun Yoo
KSPE_2025_v42n5_399_bf002.jpg
Ph.D. candidate in the Department of Mechanical Engineering, Dankook University. His research interests are fabrication and characterization of fuel cells, deposition and characterization of thin films.
Jung Soo Kim
KSPE_2025_v42n5_399_bf003.jpg
M.S. candidate in the Department of Mechanical Engineering, Dankook University. His research interests are fuel cells, fluid dynamics and thin films.
Ki Won Hong
KSPE_2025_v42n5_399_bf004.jpg
M.S. candidate in the Department of Mechanical Engineering, Dankook University. His research interests are fuel cells and thin films.
Do Young Jung
KSPE_2025_v42n5_399_bf005.jpg
M.S. candidate in the Department of Mechanical Engineering, Dankook University. His research interests are fuel cells and fluid dynamics.
George Ilhwan Park
KSPE_2025_v42n5_399_bf006.jpg
Assistant Professor in the Department of Mechanical Engineering and Applied Mechanics, University of Pennsylvania. He received his Ph.D. in Mechanical Engineering from Stanford University. His research interests are fluid dynamics and large eddy simulation.
Gu Young Cho
KSPE_2025_v42n5_399_bf007.jpg
Assistant Professor in the Department of Mechanical Engineering, Dankook University. He received his Ph.D. in Mechanical and Aerospace Engineering from Seoul National University. His research interests are fabrication and characterization of fuel cells, deposition and characterization of thin films.

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Effects of NaCl Solution on Proton Exchange Membrane Fuel Cell with Serpentine Flow Channel of Different Depths
J. Korean Soc. Precis. Eng.. 2025;42(5):399-403.   Published online May 1, 2025
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Effects of NaCl Solution on Proton Exchange Membrane Fuel Cell with Serpentine Flow Channel of Different Depths
J. Korean Soc. Precis. Eng.. 2025;42(5):399-403.   Published online May 1, 2025
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Effects of NaCl Solution on Proton Exchange Membrane Fuel Cell with Serpentine Flow Channel of Different Depths
Image Image Image Image
Fig. 1 Schematic of NaCl contamination setup
Fig. 2 Changes in electrochemical characteristics for each case
Fig. 3 Voltage changes at constant current as a function of time in 10 hours. The value of the applied current was determined by the current measured at 0.6 V in the initial IV curve
Fig. 4 EIS measurement @ 0.5 V for each case humidified with NaCl solution
Effects of NaCl Solution on Proton Exchange Membrane Fuel Cell with Serpentine Flow Channel of Different Depths
Case Humidification medium Design parameters of channel
Depth [mm] Width [mm]
1 DI water 0.8 1.0
2 NaCl solution 0.8
3 NaCl solution 0.4
4 NaCl solution 1.6
Channel depth [mm] 0.4 0.8 1.6
Degradation rate
@ Max. power [%]
2.4 5.0 7.3
Increase rate of activation
loss [%]
1.4 4.8 6.3
Table 1 Humidification medium and channel parameters of each case
Table 2 Performance changes of NaCl solution cases with different channel depths