Durability challenges and perspective in the development of PGM-free electrocatalysts for the oxygen reduction reaction
Abstract
Significant advancement in the development of highly active platinum group metal-free (PGM-free) electrocatalysts is giving rise to the possibility of a low-cost replacement for Pt electrocatalysts in polymer electrolyte fuel cells. However, before the successful implementation of PGM-free electrocatalysts, the challenge of long-term stability under fuel cell operating conditions needs to be addressed. In this paper, the current status of PGM-free electrocatalyst performance and durability is reviewed. A perspective on the route for the study of degradation mechanisms in PGM-free electrocatalysts in both half-cell and membrane electrode assembly environments is presented. The analysis of proposed degradation mechanisms suggests classification into two relevant length scales: atomic scale and macro/mesoscale. Finally, an overview of different characterization techniques (both experimental and theoretical) for studying different possible degradation mechanisms is outlined. Directly addressing the underlying mechanisms leading to loss of activity in PGM-free electrocatalysts will provide valuable insight necessary for the development of next-generation materials with improved durability capable of competing with Pt-based counterparts.
- Authors:
-
- Los Alamos National Lab. (LANL), Los Alamos, NM (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), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office
- OSTI Identifier:
- 1459825
- Alternate Identifier(s):
- OSTI ID: 1701917
- Report Number(s):
- LA-UR-18-21822
Journal ID: ISSN 2451-9103
- Grant/Contract Number:
- AC52-06NA25396
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Current Opinion in Electrochemistry
- Additional Journal Information:
- Journal Volume: 9; Journal ID: ISSN 2451-9103
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Martinez, Ulises, Babu, Siddharth Komini, Holby, Edward F., and Zelenay, Piotr. Durability challenges and perspective in the development of PGM-free electrocatalysts for the oxygen reduction reaction. United States: N. p., 2018.
Web. doi:10.1016/j.coelec.2018.04.010.
Martinez, Ulises, Babu, Siddharth Komini, Holby, Edward F., & Zelenay, Piotr. Durability challenges and perspective in the development of PGM-free electrocatalysts for the oxygen reduction reaction. United States. https://doi.org/10.1016/j.coelec.2018.04.010
Martinez, Ulises, Babu, Siddharth Komini, Holby, Edward F., and Zelenay, Piotr. 2018.
"Durability challenges and perspective in the development of PGM-free electrocatalysts for the oxygen reduction reaction". United States. https://doi.org/10.1016/j.coelec.2018.04.010. https://www.osti.gov/servlets/purl/1459825.
@article{osti_1459825,
title = {Durability challenges and perspective in the development of PGM-free electrocatalysts for the oxygen reduction reaction},
author = {Martinez, Ulises and Babu, Siddharth Komini and Holby, Edward F. and Zelenay, Piotr},
abstractNote = {Significant advancement in the development of highly active platinum group metal-free (PGM-free) electrocatalysts is giving rise to the possibility of a low-cost replacement for Pt electrocatalysts in polymer electrolyte fuel cells. However, before the successful implementation of PGM-free electrocatalysts, the challenge of long-term stability under fuel cell operating conditions needs to be addressed. In this paper, the current status of PGM-free electrocatalyst performance and durability is reviewed. A perspective on the route for the study of degradation mechanisms in PGM-free electrocatalysts in both half-cell and membrane electrode assembly environments is presented. The analysis of proposed degradation mechanisms suggests classification into two relevant length scales: atomic scale and macro/mesoscale. Finally, an overview of different characterization techniques (both experimental and theoretical) for studying different possible degradation mechanisms is outlined. Directly addressing the underlying mechanisms leading to loss of activity in PGM-free electrocatalysts will provide valuable insight necessary for the development of next-generation materials with improved durability capable of competing with Pt-based counterparts.},
doi = {10.1016/j.coelec.2018.04.010},
url = {https://www.osti.gov/biblio/1459825},
journal = {Current Opinion in Electrochemistry},
issn = {2451-9103},
number = ,
volume = 9,
place = {United States},
year = {Thu Apr 26 00:00:00 EDT 2018},
month = {Thu Apr 26 00:00:00 EDT 2018}
}
Web of Science
Works referenced in this record:
Electrocatalyst approaches and challenges for automotive fuel cells
journal, June 2012
- Debe, Mark K.
- Nature, Vol. 486, Issue 7401
Recent Advances in Electrocatalysts for Oxygen Reduction Reaction
journal, February 2016
- Shao, Minhua; Chang, Qiaowan; Dodelet, Jean-Pol
- Chemical Reviews, Vol. 116, Issue 6
Recent progress on nitrogen/carbon structures designed for use in energy and sustainability applications
journal, January 2014
- Wood, Kevin N.; O'Hayre, Ryan; Pylypenko, Svitlana
- Energy Environ. Sci., Vol. 7, Issue 4
Recent progress in non-precious metal catalysts for PEM fuel cell applications
journal, July 2013
- Higgins, Drew C.; Chen, Zhongwei
- The Canadian Journal of Chemical Engineering, Vol. 91, Issue 12
A New Fuel Cell Cathode Catalyst
journal, March 1964
- Jasinski, Raymond
- Nature, Vol. 201, Issue 4925, p. 1212-1213
Heat-treated polyacrylonitrile-based catalysts for oxygen electroreduction
journal, January 1989
- Gupta, S.; Tryk, D.; Bae, I.
- Journal of Applied Electrochemistry, Vol. 19, Issue 1, p. 19-27
High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt
journal, April 2011
- Wu, G.; More, K. L.; Johnston, C. M.
- Science, Vol. 332, Issue 6028, p. 443-447
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
Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst
journal, August 2017
- Chung, Hoon T.; Cullen, David A.; Higgins, Drew
- Science, Vol. 357, Issue 6350
Highly stable precious metal-free cathode catalyst for fuel cell application
journal, September 2016
- Serov, Alexey; Workman, Michael J.; Artyushkova, Kateryna
- Journal of Power Sources, Vol. 327
A review of the stability and durability of non-precious metal catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells
journal, July 2015
- Banham, Dustin; Ye, Siyu; Pei, Katie
- Journal of Power Sources, Vol. 285
Iron-Based Catalysts with Improved Oxygen Reduction Activity in Polymer Electrolyte Fuel Cells
journal, April 2009
- Lefèvre, Michel; Proietti, Eric; Jaouen, Frédéric
- Science, Vol. 324, Issue 5923, p. 71-74
Heat-Treated Fe/N/C Catalysts for O2 Electroreduction: Are Active Sites Hosted in Micropores?
journal, March 2006
- Jaouen, Frédéric; Lefèvre, Michel; Dodelet, Jean-Pol
- The Journal of Physical Chemistry B, Vol. 110, Issue 11, p. 5553-5558
Mesoporous Metal–Nitrogen-Doped Carbon Electrocatalysts for Highly Efficient Oxygen Reduction Reaction
journal, October 2013
- Liang, Hai-Wei; Wei, Wei; Wu, Zhong-Shuai
- Journal of the American Chemical Society, Vol. 135, Issue 43
Highly active oxygen reduction non-platinum group metal electrocatalyst without direct metal–nitrogen coordination
journal, June 2015
- Strickland, Kara; Miner, Elise; Jia, Qingying
- Nature Communications, Vol. 6, Issue 1
Highly efficient nonprecious metal catalyst prepared with metal–organic framework in a continuous carbon nanofibrous network
journal, August 2015
- Shui, Jianglan; Chen, Chen; Grabstanowicz, Lauren
- Proceedings of the National Academy of Sciences, Vol. 112, Issue 34
Engineering nanostructures of PGM-free oxygen-reduction catalysts using metal-organic frameworks
journal, January 2017
- Zhang, Hanguang; Osgood, Hannah; Xie, Xiaohong
- Nano Energy, Vol. 31
Structural and mechanistic basis for the high activity of Fe–N–C catalysts toward oxygen reduction
journal, January 2016
- Li, Jingkun; Ghoshal, Shraboni; Liang, Wentao
- Energy & Environmental Science, Vol. 9, Issue 7
Structural Descriptors of Zeolitic–Imidazolate Frameworks Are Keys to the Activity of Fe–N–C Catalysts
journal, December 2016
- Armel, Vanessa; Hindocha, Sheena; Salles, Fabrice
- Journal of the American Chemical Society, Vol. 139, Issue 1
Is iron involved in the lack of stability of Fe/N/C electrocatalysts used to reduce oxygen at the cathode of PEM fuel cells?
journal, November 2016
- Zhang, Gaixia; Chenitz, Régis; Lefèvre, Michel
- Nano Energy, Vol. 29
In Situ Polymer Graphenization Ingrained with Nanoporosity in a Nitrogenous Electrocatalyst Boosting the Performance of Polymer-Electrolyte-Membrane Fuel Cells
journal, December 2016
- Fu, Xiaogang; Zamani, Pouyan; Choi, Ja-Yeon
- Advanced Materials, Vol. 29, Issue 7
Is the rapid initial performance loss of Fe/N/C non precious metal catalysts due to micropore flooding?
journal, January 2017
- Choi, Ja-Yeon; Yang, Lijun; Kishimoto, Takeaki
- Energy & Environmental Science, Vol. 10, Issue 1
Recent development of non-platinum catalysts for oxygen reduction reaction
journal, December 2005
- Wang, Bin
- Journal of Power Sources, Vol. 152, p. 1-15
Minimizing Operando Demetallation of Fe-N-C Electrocatalysts in Acidic Medium
journal, April 2016
- Choi, Chang Hyuck; Baldizzone, Claudio; Polymeros, George
- ACS Catalysis, Vol. 6, Issue 5
A specific demetalation of Fe–N 4 catalytic sites in the micropores of NC_Ar + NH 3 is at the origin of the initial activity loss of the highly active Fe/N/C catalyst used for the reduction of oxygen in PEM fuel cells
journal, January 2018
- Chenitz, Régis; Kramm, Ulrike I.; Lefèvre, Michel
- Energy & Environmental Science, Vol. 11, Issue 2
Fe-based catalysts for the reduction of oxygen in polymer electrolyte membrane fuel cell conditions: determination of the amount of peroxide released during electroreduction and its influence on the stability of the catalysts
journal, August 2003
- Lefèvre, Michel; Dodelet, Jean-Pol
- Electrochimica Acta, Vol. 48, Issue 19, p. 2749-2760
Catalysts for the Oxygen Reduction from Heat-Treated Iron(III) Tetramethoxyphenylporphyrin Chloride: Structure and Stability of Active Sites
journal, August 2003
- Schulenburg, Hendrik; Stankov, Svetoslav; Schünemann, Volker
- The Journal of Physical Chemistry B, Vol. 107, Issue 34, p. 9034-9041
Degradation by Hydrogen Peroxide of Metal-Nitrogen-Carbon Catalysts for Oxygen Reduction
journal, January 2015
- Goellner, Vincent; Armel, Vanessa; Zitolo, Andrea
- Journal of The Electrochemical Society, Vol. 162, Issue 6
Unveiling N-Protonation and Anion-Binding Effects on Fe/N/C Catalysts for O 2 Reduction in Proton-Exchange-Membrane Fuel Cells
journal, July 2011
- Herranz, Juan; Jaouen, Frédéric; Lefèvre, Michel
- The Journal of Physical Chemistry C, Vol. 115, Issue 32
Stability of Fe-N-C Catalysts in Acidic Medium Studied by Operando Spectroscopy
journal, August 2015
- Choi, Chang Hyuck; Baldizzone, Claudio; Grote, Jan-Philipp
- Angewandte Chemie International Edition, Vol. 54, Issue 43
Structure of Fe–N x –C Defects in Oxygen Reduction Reaction Catalysts from First-Principles Modeling
journal, June 2014
- Holby, Edward F.; Wu, Gang; Zelenay, Piotr
- The Journal of Physical Chemistry C, Vol. 118, Issue 26
Spectroscopic insights into the nature of active sites in iron–nitrogen–carbon electrocatalysts for oxygen reduction in acid
journal, November 2016
- Jia, Qingying; Ramaswamy, Nagappan; Tylus, Urszula
- Nano Energy, Vol. 29
Activity of N-coordinated multi-metal-atom active site structures for Pt-free oxygen reduction reaction catalysis: Role of *OH ligands
journal, March 2015
- Holby, Edward F.; Taylor, Christopher D.
- Scientific Reports, Vol. 5, Issue 1
A Combined Probe-Molecule, Mössbauer, Nuclear Resonance Vibrational Spectroscopy, and Density Functional Theory Approach for Evaluation of Potential Iron Active Sites in an Oxygen Reduction Reaction Catalyst
journal, July 2017
- Kneebone, Jared L.; Daifuku, Stephanie L.; Kehl, Jeffrey A.
- The Journal of Physical Chemistry C, Vol. 121, Issue 30
Stability of iron species in heat-treated polyaniline–iron–carbon polymer electrolyte fuel cell cathode catalysts
journal, November 2013
- Ferrandon, Magali; Wang, Xiaoping; Kropf, A. Jeremy
- Electrochimica Acta, Vol. 110
The intriguing poison tolerance of non-precious metal oxygen reduction reaction (ORR) catalysts
journal, January 2016
- Malko, D.; Lopes, T.; Symianakis, E.
- Journal of Materials Chemistry A, Vol. 4, Issue 1
Tolerance of non-platinum group metals cathodes proton exchange membrane fuel cells to air contaminants
journal, August 2016
- Reshetenko, Tatyana; Serov, Alexey; Artyushkova, Kateryna
- Journal of Power Sources, Vol. 324
Use of H 2 S to Probe the Active Sites in FeNC Catalysts for the Oxygen Reduction Reaction (ORR) in Acidic Media
journal, September 2014
- Singh, Deepika; Mamtani, Kuldeep; Bruening, Christopher R.
- ACS Catalysis, Vol. 4, Issue 10
CO Poisoning Effects on FeNC and CN x ORR Catalysts: A Combined Experimental–Computational Study
journal, July 2016
- Zhang, Qiang; Mamtani, Kuldeep; Jain, Deeksha
- The Journal of Physical Chemistry C, Vol. 120, Issue 28
Nitrogen-Doped Carbon Vesicles with Dual Iron-Based Sites for Efficient Oxygen Reduction
journal, January 2017
- Li, Qianru; Wan, Gang; Zhao, Han
- ChemSusChem, Vol. 10, Issue 3
Beyond the top of the volcano? – A unified approach to electrocatalytic oxygen reduction and oxygen evolution
journal, November 2016
- Busch, Michael; Halck, Niels B.; Kramm, Ulrike I.
- Nano Energy, Vol. 29
Carbon support oxidation in PEM fuel cell cathodes
journal, February 2008
- Maass, S.; Finsterwalder, F.; Frank, G.
- Journal of Power Sources, Vol. 176, Issue 2
Electrocatalytic Corrosion of Carbon Support in PEMFC Cathodes
journal, January 2004
- Roen, L. M.; Paik, C. H.; Jarvi, T. D.
- Electrochemical and Solid-State Letters, Vol. 7, Issue 1
A review of platinum-based catalyst layer degradation in proton exchange membrane fuel cells
journal, December 2009
- Zhang, Shengsheng; Yuan, Xiao-Zi; Hin, Jason Ng Cheng
- Journal of Power Sources, Vol. 194, Issue 2
Quantifying the density and utilization of active sites in non-precious metal oxygen electroreduction catalysts
journal, October 2015
- Sahraie, Nastaran Ranjbar; Kramm, Ulrike I.; Steinberg, Julian
- Nature Communications, Vol. 6, Issue 1
Does CO poison Fe-based catalysts for ORR?
journal, May 2010
- Birry, Laurent; Zagal, José H.; Dodelet, Jean-Pol
- Electrochemistry Communications, Vol. 12, Issue 5
In situ electrochemical quantification of active sites in Fe–N/C non-precious metal catalysts
journal, October 2016
- Malko, Daniel; Kucernak, Anthony; Lopes, Thiago
- Nature Communications, Vol. 7, Issue 1
PGM-free Fe-N-C catalysts for oxygen reduction reaction: Catalyst layer design
journal, September 2016
- Stariha, Sarah; Artyushkova, Kateryna; Workman, Michael J.
- Journal of Power Sources, Vol. 326
3D Analysis of Fuel Cell Electrocatalyst Degradation on Alternate Carbon Supports
journal, August 2017
- Sneed, Brian T.; Cullen, David A.; Reeves, Kimberly S.
- ACS Applied Materials & Interfaces, Vol. 9, Issue 35
4D in situ visualization of electrode morphology changes during accelerated degradation in fuel cells by X-ray computed tomography
journal, May 2017
- White, Robin T.; Wu, Alex; Najm, Marina
- Journal of Power Sources, Vol. 350
Resolving Electrode Morphology’s Impact on Platinum Group Metal-Free Cathode Performance Using Nano-CT of 3D Hierarchical Pore and Ionomer Distribution
journal, November 2016
- Komini Babu, Siddharth; Chung, Hoon T.; Zelenay, Piotr
- ACS Applied Materials & Interfaces, Vol. 8, Issue 48
Time Resolved Corrosion of Electrode Supports in PEM Fuel Cells
journal, March 2013
- Fairweather, J. D.; Spernjak, D.; Mukundan, R.
- ECS Transactions, Vol. 50, Issue 2
Membrane/Electrode Assembly Water Content Measured with 2 µm Spatial Resolution Neutron Imaging
journal, August 2017
- Hussey, Daniel S.; LaManna, Jacob M.; Baltic, Elias
- ECS Transactions, Vol. 80, Issue 8
Linking structure to function: The search for active sites in non-platinum group metal oxygen reduction reaction catalysts
journal, November 2016
- Holby, Edward F.; Zelenay, Piotr
- Nano Energy, Vol. 29
First-Principles Molecular Dynamics Study of Carbon Corrosion in PEFC Catalyst Materials
journal, August 2016
- Holby, E. F.
- Fuel Cells, Vol. 16, Issue 6
Modeling Electrochemical Performance of the Hierarchical Morphology of Precious Group Metal-Free Cathode for Polymer Electrolyte Fuel Cell
journal, January 2017
- Babu, S. Komini; Chung, H. T.; Zelenay, P.
- Journal of The Electrochemical Society, Vol. 164, Issue 9
Modeling of Low-Temperature Fuel Cell Electrodes Using Non-Precious Metal Catalysts
journal, January 2015
- Leonard, Nathaniel D.; Artyushkova, Kateryna; Halevi, Barr
- Journal of The Electrochemical Society, Vol. 162, Issue 10
Lattice Boltzmann Pore-Scale Investigation of Coupled Physical-electrochemical Processes in C/Pt and Non-Precious Metal Cathode Catalyst Layers in Proton Exchange Membrane Fuel Cells
journal, March 2015
- Chen, Li; Wu, Gang; Holby, Edward F.
- Electrochimica Acta, Vol. 158
Nano-structured non-platinum catalysts for automotive fuel cell application
journal, September 2015
- Serov, Alexey; Artyushkova, Kateryna; Niangar, Ellazar
- Nano Energy, Vol. 16
Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials
journal, August 2015
- Zitolo, Andrea; Goellner, Vincent; Armel, Vanessa
- Nature Materials, Vol. 14, Issue 9
Critical role of intercalated water for electrocatalytically active nitrogen-doped graphitic systems
journal, March 2016
- Martinez, Ulises; Dumont, Joseph H.; Holby, Edward F.
- Science Advances, Vol. 2, Issue 3
Elucidating Oxygen Reduction Active Sites in Pyrolyzed Metal–Nitrogen Coordinated Non-Precious-Metal Electrocatalyst Systems
journal, April 2014
- Tylus, Urszula; Jia, Qingying; Strickland, Kara
- The Journal of Physical Chemistry C, Vol. 118, Issue 17
A review of Fe–N/C and Co–N/C catalysts for the oxygen reduction reaction
journal, June 2008
- Bezerra, Cicero W.B.; Zhang, Lei; Lee, Kunchan
- Electrochimica Acta, Vol. 53, Issue 15, p. 4937-4951
Manganese-Based Non-Precious Metal Catalyst for Oxygen Reduction in Acidic Media
journal, September 2014
- Higgins, D.; Wu, G.; Chung, H. T.
- ECS Transactions, Vol. 61, Issue 31
DOE Fuel Cell Program: Durability Technical Targets and Testing Protocols
conference, January 2007
- Garland, Nancy; Benjamin, Thomas; Kopasz, John
- 212th ECS Meeting, ECS Transactions
A review of accelerated stress tests of MEA durability in PEM fuel cells
journal, January 2009
- Zhang, S.; Yuan, X.; Wang, H.
- International Journal of Hydrogen Energy, Vol. 34, Issue 1
Works referencing / citing this record:
Experimental and Theoretical Trends of PGM-Free Electrocatalysts for the Oxygen Reduction Reaction with Different Transition Metals
journal, January 2019
- Martinez, Ulises; Holby, Edward F.; Babu, Siddharth Komini
- Journal of The Electrochemical Society, Vol. 166, Issue 7
High-performance water oxidation catalysts based on the spontaneous deposition of ruthenium on electrochemically exfoliated graphene oxide
journal, January 2019
- Fruehwald, Holly M.; Moghaddam, Reza B.; Zenkina, Olena V.
- Catalysis Science & Technology, Vol. 9, Issue 23
Toward Efficient Carbon and Water Cycles: Emerging Opportunities with Single‐Site Catalysts Made of 3d Transition Metals
journal, November 2019
- Wan, Gang; Zhang, Guanghui; Lin, Xiao‐Min
- Advanced Materials, Vol. 32, Issue 2
Atomically Dispersed Iron Cathode Catalysts Derived from Binary Ligand-Based Zeolitic Imidazolate Frameworks with Enhanced Stability for PEM Fuel Cells
journal, January 2019
- Zhang, Hanguang; Ding, Shuo; Hwang, Sooyeon
- Journal of The Electrochemical Society, Vol. 166, Issue 7
Impedance Spectroscopy Characterization of PEM Fuel Cells with Fe-N-C-Based Cathodes
journal, January 2019
- Reshetenko, Tatyana; Serov, Alexey; Kulikovsky, Andrei
- Journal of The Electrochemical Society, Vol. 166, Issue 10
Methanol-Tolerant M–N–C Catalysts for Oxygen Reduction Reactions in Acidic Media and Their Application in Direct Methanol Fuel Cells
journal, December 2018
- Lo Vecchio, Carmelo; Sebastián, David; Lázaro, María
- Catalysts, Vol. 8, Issue 12
Platinum group metal-free catalysts boost cost competitiveness of fuel cell vehicles
journal, July 2019
- Thompson, Simon T.; Papageorgopoulos, Dimitrios
- Nature Catalysis, Vol. 2, Issue 7
Correlation between Precursor Properties and Performance in the Oxygen Reduction Reaction of Pt and Co “Core-shell” Carbon Nitride-Based Electrocatalysts
journal, November 2019
- Di Noto, Vito; Negro, Enrico; Nale, Angeloclaudio
- Electrocatalysis, Vol. 11, Issue 2
Integrating PGM‐Free Catalysts into Catalyst Layers and Proton Exchange Membrane Fuel Cell Devices
journal, December 2018
- Banham, Dustin; Choi, Ja‐Yeon; Kishimoto, Takeaki
- Advanced Materials, Vol. 31, Issue 31
Progress in the Development of Fe‐Based PGM‐Free Electrocatalysts for the Oxygen Reduction Reaction
journal, December 2018
- Martinez, Ulises; Komini Babu, Siddharth; Holby, Edward F.
- Advanced Materials, Vol. 31, Issue 31
PGM‐Free Cathode Catalysts for PEM Fuel Cells: A Mini‐Review on Stability Challenges
journal, December 2018
- Shao, Yuyan; Dodelet, Jean‐Pol; Wu, Gang
- Advanced Materials, Vol. 31, Issue 31