DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: The contamination mechanism and behavior of amide bond containing organic contaminant on PEMFC

Abstract

In this paper, a study is presented of the effects of an organic contaminant containing an amide bond (-CONH-), ε-caprolactam, on polymer electrolyte membrane fuel cells (PEMFCs). The ε-caprolactam has been detected in leachates from polyphthalamide materials that are being considered for use as balance-of-plant structural materials for PEMFCs. Contamination effects from ε-caprolactam in Nafion membranes are shown to be controlled by temperature. A possible explanation of the temperature effect is the endothermic ring-opening reaction of the amide bond (-NHCO-) of the cyclic ε-caprolactam. UV-vis and ATR-IR spectroscopy studies confirmed the presence of open ring structure of ε-caprolactam in membranes. The ECSA and kinetic current for the ORR of the Pt/C catalyst were also investigated and were observed to decrease upon contamination by the ε-caprolactam. By comparison of the CVs of ammonia and acetic acid, we confirmed the adsorption of carboxylic acid (-COOH) or carboxylate anion (-COO-) onto the surface of the Pt. In conclusion, a comparison of in situ voltage losses at 80°C and 50°C also revealed temperature effects, especially in the membrane, as a result of the dramatic increase in the HFR.

Authors:
 [1];  [1];  [2];  [2];  [3]
  1. Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemical Engineering
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States). Chemical and Materials Science Center
  3. Univ. of Alabama, Tuscaloosa, AL (United States). Dept. of Chemical and Biological Engineering
Publication Date:
Research Org.:
National Renewable Energy Laboratory (NREL), Golden, CO (United States); Univ. of South Carolina, Columbia, SC (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office
OSTI Identifier:
1220615
Report Number(s):
NREL/JA-5900-62537
Journal ID: ISSN 0013-4651
Grant/Contract Number:  
AC36-08GO28308; ZGB-0-99180-1
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 162; Journal Issue: 4; Related Information: Journal of the Electrochemical Society; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 77 NANOSCIENCE AND NANOTECHNOLOGY; caprolactam; absorption; organic contaminant; amide bond

Citation Formats

Cho, Hyun -Seok, Das, Mayukhee, Wang, Heli, Dinh, Huyen N., and Van Zee, J. W. The contamination mechanism and behavior of amide bond containing organic contaminant on PEMFC. United States: N. p., 2015. Web. doi:10.1149/2.0631504jes.
Cho, Hyun -Seok, Das, Mayukhee, Wang, Heli, Dinh, Huyen N., & Van Zee, J. W. The contamination mechanism and behavior of amide bond containing organic contaminant on PEMFC. United States. https://doi.org/10.1149/2.0631504jes
Cho, Hyun -Seok, Das, Mayukhee, Wang, Heli, Dinh, Huyen N., and Van Zee, J. W. Tue . "The contamination mechanism and behavior of amide bond containing organic contaminant on PEMFC". United States. https://doi.org/10.1149/2.0631504jes. https://www.osti.gov/servlets/purl/1220615.
@article{osti_1220615,
title = {The contamination mechanism and behavior of amide bond containing organic contaminant on PEMFC},
author = {Cho, Hyun -Seok and Das, Mayukhee and Wang, Heli and Dinh, Huyen N. and Van Zee, J. W.},
abstractNote = {In this paper, a study is presented of the effects of an organic contaminant containing an amide bond (-CONH-), ε-caprolactam, on polymer electrolyte membrane fuel cells (PEMFCs). The ε-caprolactam has been detected in leachates from polyphthalamide materials that are being considered for use as balance-of-plant structural materials for PEMFCs. Contamination effects from ε-caprolactam in Nafion membranes are shown to be controlled by temperature. A possible explanation of the temperature effect is the endothermic ring-opening reaction of the amide bond (-NHCO-) of the cyclic ε-caprolactam. UV-vis and ATR-IR spectroscopy studies confirmed the presence of open ring structure of ε-caprolactam in membranes. The ECSA and kinetic current for the ORR of the Pt/C catalyst were also investigated and were observed to decrease upon contamination by the ε-caprolactam. By comparison of the CVs of ammonia and acetic acid, we confirmed the adsorption of carboxylic acid (-COOH) or carboxylate anion (-COO-) onto the surface of the Pt. In conclusion, a comparison of in situ voltage losses at 80°C and 50°C also revealed temperature effects, especially in the membrane, as a result of the dramatic increase in the HFR.},
doi = {10.1149/2.0631504jes},
journal = {Journal of the Electrochemical Society},
number = 4,
volume = 162,
place = {United States},
year = {Tue Feb 03 00:00:00 EST 2015},
month = {Tue Feb 03 00:00:00 EST 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 11 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Scientific Aspects of Polymer Electrolyte Fuel Cell Durability and Degradation
journal, October 2007

  • Borup, Rod; Meyers, Jeremy; Pivovar, Bryan
  • Chemical Reviews, Vol. 107, Issue 10
  • DOI: 10.1021/cr050182l

Effect of Transient Ammonia Concentrations on PEMFC Performance
journal, January 2003

  • Soto, Herie J.; Lee, Woo-kum; Van Zee, J. W.
  • Electrochemical and Solid-State Letters, Vol. 6, Issue 7
  • DOI: 10.1149/1.1574651

An experimental approach to investigate the transport of ammonia as a fuel contaminant in proton exchange membrane fuel cells
journal, February 2015


PEM fuel cell cathode contamination in the presence of cobalt ion (Co2+)
journal, August 2010


In situ metal ion contamination and the effects on proton exchange membrane fuel cell performance
journal, November 2011


Impact of Sulfur Dioxide on the Oxygen Reduction Reaction at Pt/Vulcan Carbon Electrocatalysts
journal, January 2007

  • Garsany, Yannick; Baturina, Olga A.; Swider-Lyons, Karen E.
  • Journal of The Electrochemical Society, Vol. 154, Issue 7
  • DOI: 10.1149/1.2736648

Assessing durability of cathodes exposed to common air impurities
journal, November 2004


Quantifying the ‘reverse water gas shift’ reaction inside a PEM fuel cell
journal, March 2005


Effects of Hydrogen Sulfide on the Performance of a PEMFC
journal, January 2003

  • Mohtadi, R.; Lee, W. -k.; Cowan, S.
  • Electrochemical and Solid-State Letters, Vol. 6, Issue 12
  • DOI: 10.1149/1.1621831

Degradation of elastomeric gasket materials in PEM fuel cells
journal, February 2007


Theory for water management in membranes for polymer electrolyte fuel cells
journal, April 1999


Effect of cations (Na+, Ca2+, Fe3+) on the conductivity of a Nafion membrane
journal, November 2010


Contaminant absorption and conductivity in polymer electrolyte membranes
journal, August 2005


Conductivity of polymer electrolyte membranes by impedance spectroscopy with microelectrodes
journal, August 2005


Unprecedented Effect of Impurity Cations on the Oxygen Reduction Kinetics at Platinum Electrodes Covered with Perfluorinated Ionomer
journal, November 1999

  • Okada, Tatsuhiro; Dale, Jørgen; Ayato, Yuusuke
  • Langmuir, Vol. 15, Issue 24
  • DOI: 10.1021/la990625e

Effects of Additives on Oxygen Reduction Kinetics at the Interface between Platinum and Perfluorinated Ionomer
journal, March 2003

  • Okada, Tatsuhiro; Satou, Hiroki; Yuasa, Makoto
  • Langmuir, Vol. 19, Issue 6
  • DOI: 10.1021/la020743t

The Effect of Impurity Cations on the Oxygen Reduction Kinetics at Platinum Electrodes Covered with Perfluorinated Ionomer
journal, July 2001

  • Okada, Tatsuhiro; Ayato, Yuusuke; Satou, Hiroki
  • The Journal of Physical Chemistry B, Vol. 105, Issue 29
  • DOI: 10.1021/jp010822y

Oxygen reduction kinetics at platinum electrodes covered with perfluorinated ionomer in the presence of impurity cations Fe3+, Ni2+ and Cu2+
journal, January 2000

  • Okada, Tatsuhiro; Ayato, Yuusuke; Dale, Jørgen
  • Physical Chemistry Chemical Physics, Vol. 2, Issue 14
  • DOI: 10.1039/b002566f

Membrane transport characteristics of binary cation systems with Li+ and alkali metal cations in perfluorosulfonated ionomer
journal, May 2005


Transport and equilibrium properties of Nafion® membranes with H+ and Na+ ions
journal, January 1998

  • Okada, Tatsuhiro; Møller-Holst, Steffen; Gorseth, Oddvar
  • Journal of Electroanalytical Chemistry, Vol. 442, Issue 1-2
  • DOI: 10.1016/S0022-0728(97)00499-3

Esterification as a diagnostic tool to predict proton conductivity affected by impurities on Nafion components for proton exchange membrane fuel cells
journal, June 2010


Influence of Ammonium on Conductivity and Water Content of Nafion 117 Membranes
journal, January 2004

  • Halseid, Rune; Vie, Preben J. S.; Tunold, Reidar
  • Journal of The Electrochemical Society, Vol. 151, Issue 3
  • DOI: 10.1149/1.1641035

Water Uptake by and Transport Through Nafion® 117 Membranes
journal, January 1993

  • Zawodzinski, Thomas A.
  • Journal of The Electrochemical Society, Vol. 140, Issue 4
  • DOI: 10.1149/1.2056194

Effect of Ammonia as Potential Fuel Impurity on Proton Exchange Membrane Fuel Cell Performance
journal, January 2002

  • Uribe, Francisco A.; Gottesfeld, Shimshon; Zawodzinski, Thomas A.
  • Journal of The Electrochemical Society, Vol. 149, Issue 3
  • DOI: 10.1149/1.1447221

Influence of ammonia on membrane-electrode assemblies in polymer electrolyte fuel cells
journal, November 2009


Aniline as a Cationic and Aromatic Contaminant in PEMFCs
journal, October 2010

  • Cho, Hyun-Seok; Jung, Myunghee; Navarro, Jose
  • ECS Transactions, Vol. 33, Issue 1
  • DOI: 10.1149/1.3484652

Evaluating the Influence of PEMFC System Contaminants on the Performance of Pt Catalyst via Cyclic Voltammetry
journal, October 2013


Impact of Structural Plastics as Balance of Plant Components on Proton Exchange Membrane Fuel Cell Performance
journal, August 2013


Impact of Polymer Electrolyte Membrane Degradation Products on the Activity of the Oxygen Reduction Reaction for Platinum Catalysts
journal, March 2013


Characterizing Polymeric Leachants for Potential System Contaminants of Fuel Cells
journal, October 2010

  • Macomber, Clay; Wang, Heli; O'Neill, Kevin
  • ECS Transactions, Vol. 33, Issue 1
  • DOI: 10.1149/1.3484653

Characterizing Leachant Contaminants from Fuel Cell Assembly Aids, a Prelude to Effects on Performance
journal, March 2013


The Effect on PEMFC Contamination of Functional Groups of Some Organic Contaminants
journal, October 2011

  • Cho, Hyun-Seok; Ohashi, Masato; Van Zee, J. W.
  • ECS Transactions, Vol. 41, Issue 1
  • DOI: 10.1149/1.3635679

Isomerization Polymerization of Lactams
book, June 1977


Diagnosis of the nature of carboxylate coordination from the direction of shifts of carbonoxygen stretching frequencies
journal, October 1985


Mass transfer in Nation membrane systems: Effects of ionic size and charge on selectivity
journal, May 1991


Interaction of H2O, CH3OH, (CH3)2O, CH3CN, and Pyridine with the Superacid Perfluorosulfonic Membrane Nafion: An IR and Raman Study
journal, August 1995

  • Buzzoni, Roberto; Bordiga, Silvia; Ricchiardi, Gabriele
  • The Journal of Physical Chemistry, Vol. 99, Issue 31
  • DOI: 10.1021/j100031a023

Nanostructure of Nafion® membranes at different states of hydration
journal, November 2001


State of Understanding of Nafion
journal, October 2004

  • Mauritz, Kenneth A.; Moore, Robert B.
  • Chemical Reviews, Vol. 104, Issue 10
  • DOI: 10.1021/cr0207123

TGA and Time-Dependent FTIR Study of Dehydrating Nafion−Na Membrane
journal, February 2003

  • Wang, Yanqia; Kawano, Yoshio; Aubuchon, Steven R.
  • Macromolecules, Vol. 36, Issue 4
  • DOI: 10.1021/ma020156e

Adsorption of Carboxylic Acids on Gold by Anodic Reaction
journal, May 2003

  • Paik, Woon-kie; Han, Subong; Shin, Woonsup
  • Langmuir, Vol. 19, Issue 10
  • DOI: 10.1021/la026836s

Polymer Electrolyte Fuel Cell Model
journal, January 1991

  • Springer, T. E.
  • Journal of The Electrochemical Society, Vol. 138, Issue 8
  • DOI: 10.1149/1.2085971

Water Uptake of Perfluorosulfonic Acid Membranes from Liquid Water and Water Vapor
journal, January 1994

  • Hinatsu, James T.
  • Journal of The Electrochemical Society, Vol. 141, Issue 6
  • DOI: 10.1149/1.2054951

Works referencing / citing this record:

A Scaling Method for Correlating Ex Situ and In Situ Measurements in PEM Fuel Cells and Electrolyzer
journal, January 2018

  • Cho, Hyun-Seok; Cho, Won-Chul; Van Zee, J. W.
  • Journal of The Electrochemical Society, Vol. 165, Issue 10
  • DOI: 10.1149/2.0041811jes