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

Title: Durable and self-hydrating tungsten carbide-based composite polymer electrolyte membrane fuel cells

Abstract

Proton conductivity of the polymer electrolyte membranes in fuel cells dictates their performance and requires sufficient water management. Here, we report a simple, scalable method to produce well-dispersed transition metal carbide nanoparticles. We demonstrate that these, when added as an additive to the proton exchange Nafion membrane, provide significant enhancement in power density and durability over 100 hours, surpassing both the baseline Nafion and platinum-containing recast Nafion membranes. Using focused ion beam/scanning electron microscope tomography reveals the key membrane degradation mechanism. Density functional theory exposes that OH• and H• radicals adsorb more strongly from solution and reactions producing OH• are significantly more endergonic on tungsten carbide than on platinum. Consequently, tungsten carbide may be a promising catalyst in self-hydrating crossover gases while retarding desorption of and capturing free radicals formed at the cathode, resulting in enhanced membrane durability.

Authors:
 [1]; ORCiD logo [2];  [3];  [1];  [2];  [2];  [1];  [1]
  1. Univ. of Delaware, Newark, DE (United States). Dept. of Chemical and Biomolecular Engineering and Catalysis Center for Energy Innovation and Center for Catalytic Science and Technology
  2. Univ. of Delaware, Newark, DE (United States). Dept. of Mechanical Engineering and Center for Full Cell Research
  3. Univ. of Delaware, Newark, DE (United States). Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
Univ. of Delaware, Newark, DE (United States); Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1425195
Grant/Contract Number:  
[SC0001004]
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
[ Journal Volume: 8; Journal Issue: 1]; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 30 DIRECT ENERGY CONVERSION; Electrocatalysis; fuel cells

Citation Formats

Zheng, Weiqing, Wang, Liang, Deng, Fei, Giles, Stephen A., Prasad, Ajay K., Advani, Suresh G., Yan, Yushan, and Vlachos, Dionisios G. Durable and self-hydrating tungsten carbide-based composite polymer electrolyte membrane fuel cells. United States: N. p., 2017. Web. doi:10.1038/s41467-017-00507-6.
Zheng, Weiqing, Wang, Liang, Deng, Fei, Giles, Stephen A., Prasad, Ajay K., Advani, Suresh G., Yan, Yushan, & Vlachos, Dionisios G. Durable and self-hydrating tungsten carbide-based composite polymer electrolyte membrane fuel cells. United States. doi:10.1038/s41467-017-00507-6.
Zheng, Weiqing, Wang, Liang, Deng, Fei, Giles, Stephen A., Prasad, Ajay K., Advani, Suresh G., Yan, Yushan, and Vlachos, Dionisios G. Mon . "Durable and self-hydrating tungsten carbide-based composite polymer electrolyte membrane fuel cells". United States. doi:10.1038/s41467-017-00507-6. https://www.osti.gov/servlets/purl/1425195.
@article{osti_1425195,
title = {Durable and self-hydrating tungsten carbide-based composite polymer electrolyte membrane fuel cells},
author = {Zheng, Weiqing and Wang, Liang and Deng, Fei and Giles, Stephen A. and Prasad, Ajay K. and Advani, Suresh G. and Yan, Yushan and Vlachos, Dionisios G.},
abstractNote = {Proton conductivity of the polymer electrolyte membranes in fuel cells dictates their performance and requires sufficient water management. Here, we report a simple, scalable method to produce well-dispersed transition metal carbide nanoparticles. We demonstrate that these, when added as an additive to the proton exchange Nafion membrane, provide significant enhancement in power density and durability over 100 hours, surpassing both the baseline Nafion and platinum-containing recast Nafion membranes. Using focused ion beam/scanning electron microscope tomography reveals the key membrane degradation mechanism. Density functional theory exposes that OH• and H• radicals adsorb more strongly from solution and reactions producing OH• are significantly more endergonic on tungsten carbide than on platinum. Consequently, tungsten carbide may be a promising catalyst in self-hydrating crossover gases while retarding desorption of and capturing free radicals formed at the cathode, resulting in enhanced membrane durability.},
doi = {10.1038/s41467-017-00507-6},
journal = {Nature Communications},
number = [1],
volume = [8],
place = {United States},
year = {2017},
month = {9}
}

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

Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Nafion-Teflon-Zr(HPO[sub 4])[sub 2] Composite Membranes for High-Temperature PEMFCs
journal, January 2004

  • Si, Yongchao; Kunz, H. Russell; Fenton, James M.
  • Journal of The Electrochemical Society, Vol. 151, Issue 4
  • DOI: 10.1149/1.1651527

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Nanosized tungsten carbide synthesized by a novel route at low temperature for high performance electrocatalysis
journal, April 2013

  • Yan, Zaoxue; Cai, Mei; Shen, Pei Kang
  • Scientific Reports, Vol. 3, Issue 1
  • DOI: 10.1038/srep01646

Chemistry and materials options of sustainable carbon materials made by hydrothermal carbonization
journal, January 2010

  • Titirici, Maria-Magdalena; Antonietti, Markus
  • Chem. Soc. Rev., Vol. 39, Issue 1
  • DOI: 10.1039/B819318P

In-situ spin trap electron paramagnetic resonance study of fuel cell processes
journal, January 2004

  • Panchenko, Alexander; Dilger, Herbert; Kerres, Jochen
  • Physical Chemistry Chemical Physics, Vol. 6, Issue 11
  • DOI: 10.1039/b404253k

Hydrothermal carbon from biomass: a comparison of the local structure from poly- to monosaccharides and pentoses/hexoses
journal, January 2008

  • Titirici, Maria-Magdalena; Antonietti, Markus; Baccile, Niki
  • Green Chemistry, Vol. 10, Issue 11
  • DOI: 10.1039/b807009a

Projector augmented-wave method
journal, December 1994


Tungsten Carbide Microspheres as a Noble-Metal-Economic Electrocatalyst for Methanol Oxidation
journal, October 2005

  • Ganesan, Raman; Lee, Jae Sung
  • Angewandte Chemie International Edition, Vol. 44, Issue 40
  • DOI: 10.1002/anie.200501272

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces
journal, March 2011

  • Man, Isabela C.; Su, Hai‐Yan; Calle‐Vallejo, Federico
  • ChemCatChem, Vol. 3, Issue 7
  • DOI: 10.1002/cctc.201000397

Materials for fuel-cell technologies
journal, November 2001

  • Steele, Brian C. H.; Heinzel, Angelika
  • Nature, Vol. 414, Issue 6861, p. 345-352
  • DOI: 10.1038/35104620

Membrane degradation during combined chemical and mechanical accelerated stress testing of polymer electrolyte fuel cells
journal, July 2014


A review of polymer electrolyte membrane fuel cells: Technology, applications, and needs on fundamental research
journal, April 2011


PEM Fuel Cell Pt∕C Dissolution and Deposition in Nafion Electrolyte
journal, January 2007

  • Bi, Wu; Gray, Gary E.; Fuller, Thomas F.
  • Electrochemical and Solid-State Letters, Vol. 10, Issue 5
  • DOI: 10.1149/1.2712796

Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

N-doped carbon nanomaterials are durable catalysts for oxygen reduction reaction in acidic fuel cells
journal, February 2015


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Fuel Cells and Precious-Metal Catalysts
journal, October 1999


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

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

Experimental and Theoretical Investigation of Molybdenum Carbide and Nitride as Catalysts for Ammonia Decomposition
journal, February 2013

  • Zheng, Weiqing; Cotter, Thomas P.; Kaghazchi, Payam
  • Journal of the American Chemical Society, Vol. 135, Issue 9
  • DOI: 10.1021/ja309734u

Solution of Schrödinger’s equation for large systems
journal, December 1989

  • Teter, Michael P.; Payne, Michael C.; Allan, Douglas C.
  • Physical Review B, Vol. 40, Issue 18
  • DOI: 10.1103/PhysRevB.40.12255

Über die Entstehung der Kohlen. II. Die Inkohlung von Cellulose und Lignin in neutralem Medium
journal, January 1932


Nafion/ZrSPP composite membrane for high temperature operation of PEMFCs
journal, November 2004


Iron-based cathode catalyst with enhanced power density in polymer electrolyte membrane fuel cells
journal, August 2011

  • Proietti, Eric; Jaouen, Frédéric; Lefèvre, Michel
  • Nature Communications, Vol. 2, Issue 1
  • DOI: 10.1038/ncomms1427

A Direct Synthesis of Mesoporous Carbons with Bicontinuous Pore Morphology from Crude Plant Material by Hydrothermal Carbonization
journal, August 2007

  • Titirici, Maria M.; Thomas, Arne; Yu, Shu-Hong
  • Chemistry of Materials, Vol. 19, Issue 17
  • DOI: 10.1021/cm0707408

Self-Humidifying Polymer Electrolyte Membranes for Fuel Cells
journal, January 1996

  • Watanabe, Masahiro
  • Journal of The Electrochemical Society, Vol. 143, Issue 12
  • DOI: 10.1149/1.1837307

A Water and Heat Management Model for Proton-Exchange-Membrane Fuel Cells
journal, January 1993

  • Nguyen, Trung V.
  • Journal of The Electrochemical Society, Vol. 140, Issue 8
  • DOI: 10.1149/1.2220792

High-precision sampling for Brillouin-zone integration in metals
journal, August 1989


Nanocrack-regulated self-humidifying membranes
journal, April 2016

  • Park, Chi Hoon; Lee, So Young; Hwang, Doo Sung
  • Nature, Vol. 532, Issue 7600
  • DOI: 10.1038/nature17634

Platinum-Like Behavior of Tungsten Carbide in Surface Catalysis
journal, August 1973


Chemical Degradation of Nafion Membranes under Mimic Fuel Cell Conditions as Investigated by Solid-State NMR Spectroscopy
journal, August 2010

  • Ghassemzadeh, Lida; Kreuer, Klaus-Dieter; Maier, Joachim
  • The Journal of Physical Chemistry C, Vol. 114, Issue 34
  • DOI: 10.1021/jp102533v

Nafion® 115/zirconium phosphate composite membranes for operation of PEMFCs above 100°C
journal, January 2002


Back in the black: hydrothermal carbonization of plant material as an efficient chemical process to treat the CO2 problem?
journal, January 2007

  • Titirici, Maria-Magdalena; Thomas, Arne; Antonietti, Markus
  • New Journal of Chemistry, Vol. 31, Issue 6
  • DOI: 10.1039/b616045j

Chemical degradation of proton conducting perflurosulfonic acid ionomer membranes studied by solid-state nuclear magnetic resonance spectroscopy
journal, January 2009


Molybdenum carbide catalysts I. Synthesis of unsupported powders
journal, July 1987


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

Mechanism for Degradation of Nafion in PEM Fuel Cells from Quantum Mechanics Calculations
journal, December 2011

  • Yu, Ted H.; Sha, Yao; Liu, Wei-Guang
  • Journal of the American Chemical Society, Vol. 133, Issue 49
  • DOI: 10.1021/ja2074642

Suppression of Methanol Crossover and Distribution of Ohmic Resistance in Pt-Dispersed PEMs under DMFC Operation
journal, January 2002

  • Uchida, Hiroyuki; Mizuno, Yohsuke; Watanabe, Masahiro
  • Journal of The Electrochemical Society, Vol. 149, Issue 6
  • DOI: 10.1149/1.1471539

Nafion–TiO2 hybrid membranes for medium temperature polymer electrolyte fuel cells (PEFCs)
journal, December 2005


    Works referencing / citing this record:

    Graphitized Carbon: A Promising Stable Cathode Catalyst Support Material for Long Term PEMFC Applications
    journal, May 2018

    • Mohanta, Paritosh; Regnet, Fabian; Jörissen, Ludwig
    • Materials, Vol. 11, Issue 6
    • DOI: 10.3390/ma11060907