skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Zr-doped ceria additives for enhanced PEM fuel cell durability and radical scavenger stability

Abstract

Doped ceria compounds demonstrate excellent radical scavenging abilities and are promising additives to improve the chemical durability of polymer electrolyte membrane (PEM) fuel cells. Here in this paper, Ce0.85Zr0.15O2 (CZO) nanoparticles were incorporated into the cathode catalyst layers (CLs) of PEM fuel cells (based on Nafion XL membranes containing 6.0 μg cm-2 ion-exchanged Ce) at loadings of 10 and 55 μg cm-2. When compared to a CZO-free baseline, CZO-containing membrane electrode assemblies (MEAs) demonstrated extended lifetimes during PEM chemical stability accelerated stress tests (ASTs), exhibiting reduced electrochemical gas crossover, open circuit voltage decay, and fluoride emission rates. The MEA with high CZO loading (55 μg cm-2) demonstrated performance losses, which are attributed to Ce poisoning of the PEM and CL ionomer regions, which is supported by X-ray fluorescence (XRF) analysis. In the MEA with the low CZO loading (10 μg cm-2), both the beginning of life (BOL) performance and the performance after 500 hours of ASTs were nearly identical to the BOL performance of the CZO-free baseline MEA. XRF analysis of the MEA with low CZO loading reveals that the BOL PEM Ce concentrations are preserved after 1408 hours of ASTs and that Ce contents in the cathode CL aremore » not significant enough to reduce performance. Therefore, employing a highly effective radical scavenger such as CZO, at a loading of 10 μg cm-2 in the cathode CL, dramatically mitigates degradation effects, which improves MEA chemical durability and minimizes performance losses.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [2];  [3];  [3]; ORCiD logo [2]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Delaware, Newark, DE (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Univ. of Delaware, Newark, DE (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE). Fuel Cell Technologies Program (EE-3F)
OSTI Identifier:
1407888
Report Number(s):
LA-UR-17-23340
Journal ID: ISSN 2050-7488; TRN: US1703160
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 5; Journal Issue: 29; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Energy Sciences

Citation Formats

Baker, Andrew M., Williams, Stefan Thurston DuBard, Mukundan, Rangachary, Spernjak, Dusan, Advani, Suresh G., Prasad, Ajay K., and Borup, Rodney L. Zr-doped ceria additives for enhanced PEM fuel cell durability and radical scavenger stability. United States: N. p., 2017. Web. doi:10.1039/C7TA03452K.
Baker, Andrew M., Williams, Stefan Thurston DuBard, Mukundan, Rangachary, Spernjak, Dusan, Advani, Suresh G., Prasad, Ajay K., & Borup, Rodney L. Zr-doped ceria additives for enhanced PEM fuel cell durability and radical scavenger stability. United States. doi:10.1039/C7TA03452K.
Baker, Andrew M., Williams, Stefan Thurston DuBard, Mukundan, Rangachary, Spernjak, Dusan, Advani, Suresh G., Prasad, Ajay K., and Borup, Rodney L. Tue . "Zr-doped ceria additives for enhanced PEM fuel cell durability and radical scavenger stability". United States. doi:10.1039/C7TA03452K. https://www.osti.gov/servlets/purl/1407888.
@article{osti_1407888,
title = {Zr-doped ceria additives for enhanced PEM fuel cell durability and radical scavenger stability},
author = {Baker, Andrew M. and Williams, Stefan Thurston DuBard and Mukundan, Rangachary and Spernjak, Dusan and Advani, Suresh G. and Prasad, Ajay K. and Borup, Rodney L.},
abstractNote = {Doped ceria compounds demonstrate excellent radical scavenging abilities and are promising additives to improve the chemical durability of polymer electrolyte membrane (PEM) fuel cells. Here in this paper, Ce0.85Zr0.15O2 (CZO) nanoparticles were incorporated into the cathode catalyst layers (CLs) of PEM fuel cells (based on Nafion XL membranes containing 6.0 μg cm-2 ion-exchanged Ce) at loadings of 10 and 55 μg cm-2. When compared to a CZO-free baseline, CZO-containing membrane electrode assemblies (MEAs) demonstrated extended lifetimes during PEM chemical stability accelerated stress tests (ASTs), exhibiting reduced electrochemical gas crossover, open circuit voltage decay, and fluoride emission rates. The MEA with high CZO loading (55 μg cm-2) demonstrated performance losses, which are attributed to Ce poisoning of the PEM and CL ionomer regions, which is supported by X-ray fluorescence (XRF) analysis. In the MEA with the low CZO loading (10 μg cm-2), both the beginning of life (BOL) performance and the performance after 500 hours of ASTs were nearly identical to the BOL performance of the CZO-free baseline MEA. XRF analysis of the MEA with low CZO loading reveals that the BOL PEM Ce concentrations are preserved after 1408 hours of ASTs and that Ce contents in the cathode CL are not significant enough to reduce performance. Therefore, employing a highly effective radical scavenger such as CZO, at a loading of 10 μg cm-2 in the cathode CL, dramatically mitigates degradation effects, which improves MEA chemical durability and minimizes performance losses.},
doi = {10.1039/C7TA03452K},
journal = {Journal of Materials Chemistry. A},
number = 29,
volume = 5,
place = {United States},
year = {2017},
month = {6}
}

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

Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Fuel Cell Durability Enhancement with Cerium Oxide under Combined Chemical and Mechanical Membrane Degradation
journal, January 2015

  • Lim, C.; Alavijeh, A. S.; Lauritzen, M.
  • ECS Electrochemistry Letters, Vol. 4, Issue 4
  • DOI: 10.1149/2.0081504eel

Effect of CeOx Crystallite Size on the Chemical Stability of CeOx Nanoparticles
journal, January 2014

  • Banham, Dustin; Ye, Siyu; Cheng, Tommy
  • Journal of The Electrochemical Society, Vol. 161, Issue 10
  • DOI: 10.1149/2.0931410jes

Thin-film catalyst layers for polymer electrolyte fuel cell electrodes
journal, January 1992

  • Wilson, M. S.; Gottesfeld, S.
  • Journal of Applied Electrochemistry, Vol. 22, Issue 1
  • DOI: 10.1007/BF01093004

Degradation reduction of polymer electrolyte membranes using CeO2 as a free-radical scavenger in catalyst layer
journal, October 2013


Overcoming Artifacts in Cyclic Voltammetry through the Use of Multiple Scan Rates and Potential Windows
conference, January 2011

  • Edmundson, Mark; Busby, F. Colin
  • 220th ECS Meeting, ECS Transactions
  • DOI: 10.1149/1.3635600

Cerium Migration in Polymer Electrolyte Membranes
journal, August 2016


Cerium Migration during PEM Fuel Cell Accelerated Stress Testing
journal, January 2016

  • Baker, Andrew M.; Mukundan, Rangachary; Spernjak, Dusan
  • Journal of The Electrochemical Society, Vol. 163, Issue 9
  • DOI: 10.1149/2.0181609jes

Interactive Effects of Membrane Additives on PEMFC Catalyst Layer Degradation
journal, November 2012

  • Cheng, Tommy T. H.; Wessel, Silvia; Knights, Shanna
  • Journal of The Electrochemical Society, Vol. 160, Issue 1
  • DOI: 10.1149/2.056301jes

The Chemistry of Fuel Cell Membrane Chemical Degradation
conference, January 2008


Present status and future prospect of design of Pt–cerium oxide electrodes for fuel cell applications
journal, December 2012

  • Mori, Toshiyuki; Ou, Ding Rong; Zou, Jin
  • Progress in Natural Science: Materials International, Vol. 22, Issue 6
  • DOI: 10.1016/j.pnsc.2012.11.010

Mechanical Degradation Behavior of Recast Composite PFSA Membrane and Nafion® N-112 Membrane under OCV Condition
conference, January 2008

  • Huang, Xinyu; Rodgers, Marianne; Yoon, Wonseok
  • 214th ECS Meeting, ECS Transactions
  • DOI: 10.1149/1.2981997

CeO 2 Surface Oxygen Vacancy Concentration Governs in Situ Free Radical Scavenging Efficacy in Polymer Electrolytes
journal, September 2012

  • Trogadas, Panagiotis; Parrondo, Javier; Ramani, Vijay
  • ACS Applied Materials & Interfaces, Vol. 4, Issue 10
  • DOI: 10.1021/am3016069

Ceria and Doped Ceria Nanoparticle Additives for Polymer Fuel Cell Lifetime Improvement
journal, August 2014


Fuel Cell Perfluorinated Sulfonic Acid Membrane Degradation Correlating Accelerated Stress Testing and Lifetime
journal, September 2012

  • Rodgers, Marianne P.; Bonville, Leonard J.; Kunz, H. Russell
  • Chemical Reviews, Vol. 112, Issue 11
  • DOI: 10.1021/cr200424d

Mitigation of PFSA membrane chemical degradation using composite cerium oxide–PFSA nanofibres
journal, January 2017

  • Zatoń, M.; Rozière, J.; Jones, D. J.
  • Journal of Materials Chemistry A, Vol. 5, Issue 11
  • DOI: 10.1039/C6TA10977B

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

Degradation Mitigation in Polymer Electrolyte Membranes Using Cerium Oxide as a Regenerative Free-Radical Scavenger
journal, January 2008

  • Trogadas, Panagiotis; Parrondo, Javier; Ramani, Vijay
  • Electrochemical and Solid-State Letters, Vol. 11, Issue 7
  • DOI: 10.1149/1.2916443

Catalytic Properties of Ceria and CeO 2 -Containing Materials
journal, November 1996


Meliorated oxygen reduction reaction of polymer electrolyte membrane fuel cell in the presence of cerium–zirconium oxide
journal, September 2011

  • Sarada, B. Yamini; Dhathathreyan, K. S.; Rama Krishna, M.
  • International Journal of Hydrogen Energy, Vol. 36, Issue 18
  • DOI: 10.1016/j.ijhydene.2011.06.027

Cerium Oxide Decorated Polymer Nanofibers as Effective Membrane Reinforcement for Durable, High‐Performance Fuel Cells
journal, December 2016

  • Breitwieser, Matthias; Klose, Carolin; Hartmann, Armin
  • Advanced Energy Materials, Vol. 7, Issue 6
  • DOI: 10.1002/aenm.201602100

Mitigation of Perfluorosulfonic Acid Membrane Chemical Degradation Using Cerium and Manganese Ions
conference, January 2008

  • Coms, Frank D.; Liu, Han; Owejan, Jeanette E.
  • 214th ECS Meeting, ECS Transactions
  • DOI: 10.1149/1.2982015

The degradation mitigation effect of cerium oxide in polymer electrolyte membranes in extended fuel cell durability tests
journal, March 2013


Cerium Migration during PEM Fuel Cell Assembly and Operation
journal, September 2015


Activity of oxygen reduction reaction on small amount of amorphous CeOx promoted Pt cathode for fuel cell application
journal, April 2011


Cerium Migration through Hydrogen Fuel Cells during Accelerated Stress Testing
journal, January 2014

  • Stewart, S. M.; Spernjak, D.; Borup, R.
  • ECS Electrochemistry Letters, Vol. 3, Issue 4
  • DOI: 10.1149/2.008404eel

Radical (HO●, H● and HOO●) Formation and Ionomer Degradation in Polymer Electrolyte Fuel Cells
journal, January 2011

  • Gubler, Lorenz; Dockheer, Sindy M.; Koppenol, Willem H.
  • Journal of The Electrochemical Society, Vol. 158, Issue 7
  • DOI: 10.1149/1.3581040

Advanced materials for improved PEMFC performance and life
journal, May 2004