Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
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H2S Poisoning Effect and Recovery Methods of Polymer Electrolyte Membrane Fuel Cell

황화수소 피독이 고분자전해질 연료전지에 미치는 영향과 회복기법

  • Chun, Byungdo (School of Chemical Engineering, University of Ulsan) ;
  • Kim, Junbom (School of Chemical Engineering, University of Ulsan)
  • Received : 2016.11.28
  • Accepted : 2017.01.19
  • Published : 2017.02.01
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Abstract

The performance of polymer electrolyte membrane fuel cell (PEMFC) could be deteriorated when fuel contains contaminants such as carbon monoxide (CO) or hydrogen sulfide ($H_2S$). Generally, $H_2S$ is introduced in hydrogen by steam reforming of hydrocarbon which has mercaptan as odorant. $H_2S$ poisoning effect on PEMFC performance was examined on this study. Pure hydrogen injection, voltage cycling and water circulation methods were compared as performance recovery methods. The PEMFC performance was analyzed using electrochemical methods such as polarization curve, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). Pure hydrogen injection and voltage cycling methods showed low recovery ratio, however, water circulation method showed high recovery ratio over 95%. Because anode was directly poisoned by $H_2S$, anode water circulation showed higher recovery ratio compared to the other methods. Water circulation method was developed to recover PEMFC performance from $H_2S$ poisoning. This method could contribute to PEMFC durability and commercialization.

고분자전해질 연료전지(PEMFC: polymer electrolyte membrane fuel cell)는 일산화탄소(CO)나 황화수소($H_2S$)가 포함된 연료가 주입될 경우 성능이 저하된다. 일반적으로 멀캅탄 계열의 부취제가 첨가된 탄화수소를 개질하여 생성된 수소에는 미량의 황화수소가 포함되어 있다. 본 연구에서는 황화수소를 수소에 첨가하여 anode에 주입하였을 경우에 연료전지 성능에 미치는 영향을 파악하고, 3가지 다른 회복방법인 순수 수소 주입법, 전위 순환법과 물 순환법을 적용한 경우의 회복률을 비교하여 보았다. PEMFC의 성능은 전기화학적 방법인 polarization curve, electrochemical impedance spectroscopy (EIS)와 cyclic voltammetry (CV)를 사용하여 분석하였다. 피독에 대한 회복방법인 순수 수소 주입법과 전위 순환법을 사용한 경우에는 회복률이 적었고, 물 순환법을 사용한 경우에는 초기에 대비하여 약 95% 이상 성능이 회복된 것을 확인하였다. 직접적으로 피독에 노출된 anode에 물을 흘린 경우의 성능회복률이 높았으며, cathode에 흘린 경우에도 물의 crossover에 의한 효과로 전위 순환법보다 우수한 회복률을 보였다. 이러한 연구결과로부터 황화수소 피독에 대한 회복기법을 구축함으로서 연료전지의 내구성을 향상시킬 수 있고, 불순물이 미량 함유된 저가 수소의 사용을 가능하게 함으로서 연료전지 보급에도 기여할 수 있을 것이다.

Keywords

References

  1. Vishnyakov, V. M., "Proton Exchange Membrane Fuel Cells," Vacuum, 80(10), 1053-1065(2006). https://doi.org/10.1016/j.vacuum.2006.03.029
  2. Ralph, T. R., "Clean Fuel Cell Energy for Today," Platinum Met. Rev., 43(1), 14-17(1999).
  3. Appleby, A. J., "The Electrochemical Engine for Vehicles," Sci. Am., 281, 74-79(1999).
  4. A. C. Lloyd, "The Power Plant in Your Basement," Sci. Am., 281, 80-86(1999).
  5. C. K. Dyer, "Replacing the Battery in Portable Electronics," Sci. Am., 281, 88-93(1999).
  6. Lee, D. Y. and Hwang, S. W., "Effect of Loading and Distributions of Nafion Ionomer in the Catalyst Layer for PEMFCs," Int. J. Hydrogen Energy, 33(11), 2790-2794(2009). https://doi.org/10.1016/j.ijhydene.2008.03.046
  7. Yu, X. and Ye, S., "Recent Advances in Activity and Durability Enhancement of Pt/C Catalytic Cathode in PEMFC: Part II: Degradation Mechanism and Durability Enhancement of Carbon Supported Platinum Catalyst," J. Power Sources, 172, 145-154(2007). https://doi.org/10.1016/j.jpowsour.2007.07.048
  8. Knights, S. D., Colbow, K. M., St-Pierre, J. and Wilkinson, D. P., "Aging Mechanisms and Lifetime of PEFC and DMFC," J. Power Sources, 127, 127-134(2004). https://doi.org/10.1016/j.jpowsour.2003.09.033
  9. Stevens, D. A. and Dahn, J. R., "Thermal Degradation of the Support in Carbon-supported Platinum Electrocatalysts for PEM Fuel Cells," Carbon, 43, 179-188(2005). https://doi.org/10.1016/j.carbon.2004.09.004
  10. Jeong, J. H. and Song, M. H., "Performance and Durability of PEMFC MEAs Fabricated by Various Methods," Korean Chem. Eng. Res., 52(5), 558-563(2014). https://doi.org/10.9713/kcer.2014.52.5.558
  11. Park, S. K. and Popov, B. N., "Effect of Membrane-electrodeassembly Configuration on Proton Exchange Membrane Fuel Cell Performance," Korean J. Chem. Eng., 31(8), 1384-1388(2014). https://doi.org/10.1007/s11814-014-0037-z
  12. Park, S. M. and T. J. O'Brien, "Effects of Several Trace Contaminants on Fuel Cell Performance," Technical Report (# DOE/METC/RI-80/16), Department of Energy, Morgantown, WV, USA, 1979.
  13. P. R. Hayter, P. Mitchell, R. A. J. Dams, C. Dudfield, and N. Gladding, "The Effect of Contaminants in the Fuel and Air Streams on the Performance of a Solid Polymer Fuel Cell," Contract Report (ETSUF/02/00126/REP), Wellman CJB Limited, Portsmouth, UK, 1997.
  14. Lee, H. and Song, J. H., "Decrease of PEMFC Performance by $SO_2$ in Air," Korean Chem. Eng. Res., 48(3), 311-315(2010).
  15. Lee, H. and Song, J. H., "Decrease of PEMFC Performance by Toluene in Air," Korean Chem. Eng. Res., 49(1), 15-20(2011). https://doi.org/10.9713/kcer.2011.49.1.015
  16. Murthy, M., Esayian, M., Lee, W. K. and Van Zee J. W., "The Effect of Temperature and Pressure on the Performance of a PEMFC Exposed to Transient CO Concentrations," J. Electrochem. Soc., 150, A29-A34(2003). https://doi.org/10.1149/1.1522383
  17. Giorgi, L., Pozio, A., Bracchini, C., Giorgi, R. and Turtu, S., "$H_2$ and $H_2$/CO Oxidation Mechanism on Pt/C, Ru/C and Pt-Ru/C Electrocatalysts," J. Appl. Electrochem., 31(3) 325-334(2001). https://doi.org/10.1023/A:1017595920726
  18. Fuel Cell Handbook, 5th ed. US Department of Energy, West Virginia, 2000.
  19. Loucka, T., "Adsorption and Oxidation of Sulfur and of Sulfur Dioxide at the Platinum Electrode," J. Electroanal. Chem., 31(2), 319-332(1971). https://doi.org/10.1016/S0022-0728(71)80162-6
  20. Contractor, A. Q. and Lal, H., "Two Forms of Chemisorbed Sulfur on Platinum and Related Studies," J. Electroanal. Chem., 96(2), 175-181(1979). https://doi.org/10.1016/S0022-0728(79)80374-5
  21. Mohtadi, R., Lee, W. K. and Van Zee, J. W., "The Effect of Temperature on the Adsorption Rate of Hydrogen Sulfide on Pt Anodes in a PEMFC," Appl. Catal. B: Environmental, 56, 37-42(2005). https://doi.org/10.1016/j.apcatb.2004.08.012
  22. Shi, W., Yi, B., Hou, M., Jing, F., Yu, H. and Ming, P., "The Influence of Hydrogen Sulfide on Proton Exchange Membrane Fuel Cell Anodes," J. Power Sources, 164, 272-277(2007). https://doi.org/10.1016/j.jpowsour.2006.09.073
  23. Shi, W., Yi, B., Hou, M. and Shao, Z., "The Effect of $H_2S$ and CO Mixtures on PEMFC Performance," J. Hydrogen Energy, 32(17), 4412-4417(2007). https://doi.org/10.1016/j.ijhydene.2007.06.029
  24. Knight, S., Jia, N., Chuy, C. and Zhang, J., "Fuel Cell Seminar 2005: Fuel Cell Progress," Challenges and Markets, Palm Springs, California (2005).
  25. Shah, A. A. and Walsh, F. C., "A Model for Hydrogen Sulfide Poisoning in Proton Exchange Membrane Fuel Cells," J. Power Sources, 185(1) 287-301(2008). https://doi.org/10.1016/j.jpowsour.2008.06.082
  26. Li, L. and King, D. L., "$H_2S$ Removal with ZnO During Fuel Processing for PEM Fuel Cell Applications," Catalysis Today, 116(4), 537-541(2006). https://doi.org/10.1016/j.cattod.2006.06.024
  27. Pillay, D., Johannes, M. D., "Comparison of Sulfur Interaction with Hydrogen on Pt(111), Ni(111) and $Pt_3Ni(111)$ Surfaces: The Effect of Intermetallic Bonding," Surface Science, 602, 2752-2757 (2008). https://doi.org/10.1016/j.susc.2008.06.035
  28. Mohtadi, R., Lee, W. K. and Murthy, M., "Effects of Hydrogen Sulfide on the Performance of a PEMFC," Electrochem. Solid-State Letters, 6(12) A272-A274(2003). https://doi.org/10.1149/1.1621831
  29. Sim, W. J. and Kim, D. H., "Effects of Ru/C Catalyst on the CO Tolerance of Anode and Durability of Membrane in PEMFC," Korean Chem. Eng. Res., 46(2), 286-290(2008).
  30. Mohtadi, R. and Van Zee, J. W., "Assessing Durability of Cathodes Exposed to Common Air Impurities," J. Power Sources, 138, 216-225(2004). https://doi.org/10.1016/j.jpowsour.2004.06.036
  31. Kakati, B. K. and Kucernak, R. J., Gas Phase Recovery of Hydrogen Sulfide Contaminated Polymer Electrolyte Membrane Fuel Cells," J. Power Sources, 252, 317-326(2014). https://doi.org/10.1016/j.jpowsour.2013.11.077