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

Title: Design of PGM-free cathodic catalyst layers for advanced PEM fuel cells

Abstract

Here, the design of cathodic catalysts layer (CCL) consisted of Platinum Group Metal-free (PGM-free) electrocatalysts was done by catalyst coated membrane approach. Three different Fe-Mn-N-C compounds were synthesized with Fe:Mn ratio of 1:1, 2:1 and 2:1 with modified heat treatment profile. The catalysts were characterized by X-ray photoelectron spectroscopy, X-ray powder diffraction, pore and particle size distribution, zeta potential and transmission electron microscopy. Electrocatalysts were integrated into membrane electrode assembly and evaluated by electrochemical methods. Electrochemical impedance spectroscopy in combination with modeling were used for estimation of proton conductivity of CCL and its oxygen diffusivity. It was found that all CCLs possess extremely high proton conductivity, which was demonstrated for the first time for these types of PGM-free catalysts. The observed ORR mechanism was predominantly 4e- due to peroxide/radicals scavenging effect of Mn.

Authors:
 [1];  [2];  [3];  [1];  [1];  [4];  [5]; ORCiD logo [5]; ORCiD logo [5]; ORCiD logo [5];  [6]
  1. Univ. of Hawaii, Honolulu, HI (United States)
  2. IRD Fuel Cells, Albuquerque, NM (United States)
  3. GRandalytics, Honolulu, HI (United States)
  4. Pajarito Powder LLC, Albuquerque, NM (United States)
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  6. Forschungszentrum Jülich GmbH (Germany)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); US Department of the Navy, Office of Naval Research (ONR); Hawaiian Electric Company; USDOE Office of Science (SC)
OSTI Identifier:
1866686
Alternate Identifier(s):
OSTI ID: 1864607
Grant/Contract Number:  
AC05-00OR22725; N00014-18-1-2127; N00014-19-1-2159; EE0008419
Resource Type:
Accepted Manuscript
Journal Name:
Applied Catalysis. B, Environmental
Additional Journal Information:
Journal Volume: 312; Journal Issue: NA; Journal ID: ISSN 0926-3373
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; PEM fuel cell; PGM-free electrode; proton conductivity; electron conductivity; impedance; modeling

Citation Formats

Reshetenko, Tatyana, Odgaard, Madeleine, Randolf, Günter, Ohtaki, Kenta K., Bradley, John P., Zulevi, Barr, Lyu, Xiang, Cullen, David A., Jafta, Charl J., Serov, Alexey, and Kulikovsky, Andrei. Design of PGM-free cathodic catalyst layers for advanced PEM fuel cells. United States: N. p., 2022. Web. doi:10.1016/j.apcatb.2022.121424.
Reshetenko, Tatyana, Odgaard, Madeleine, Randolf, Günter, Ohtaki, Kenta K., Bradley, John P., Zulevi, Barr, Lyu, Xiang, Cullen, David A., Jafta, Charl J., Serov, Alexey, & Kulikovsky, Andrei. Design of PGM-free cathodic catalyst layers for advanced PEM fuel cells. United States. https://doi.org/10.1016/j.apcatb.2022.121424
Reshetenko, Tatyana, Odgaard, Madeleine, Randolf, Günter, Ohtaki, Kenta K., Bradley, John P., Zulevi, Barr, Lyu, Xiang, Cullen, David A., Jafta, Charl J., Serov, Alexey, and Kulikovsky, Andrei. Wed . "Design of PGM-free cathodic catalyst layers for advanced PEM fuel cells". United States. https://doi.org/10.1016/j.apcatb.2022.121424. https://www.osti.gov/servlets/purl/1866686.
@article{osti_1866686,
title = {Design of PGM-free cathodic catalyst layers for advanced PEM fuel cells},
author = {Reshetenko, Tatyana and Odgaard, Madeleine and Randolf, Günter and Ohtaki, Kenta K. and Bradley, John P. and Zulevi, Barr and Lyu, Xiang and Cullen, David A. and Jafta, Charl J. and Serov, Alexey and Kulikovsky, Andrei},
abstractNote = {Here, the design of cathodic catalysts layer (CCL) consisted of Platinum Group Metal-free (PGM-free) electrocatalysts was done by catalyst coated membrane approach. Three different Fe-Mn-N-C compounds were synthesized with Fe:Mn ratio of 1:1, 2:1 and 2:1 with modified heat treatment profile. The catalysts were characterized by X-ray photoelectron spectroscopy, X-ray powder diffraction, pore and particle size distribution, zeta potential and transmission electron microscopy. Electrocatalysts were integrated into membrane electrode assembly and evaluated by electrochemical methods. Electrochemical impedance spectroscopy in combination with modeling were used for estimation of proton conductivity of CCL and its oxygen diffusivity. It was found that all CCLs possess extremely high proton conductivity, which was demonstrated for the first time for these types of PGM-free catalysts. The observed ORR mechanism was predominantly 4e- due to peroxide/radicals scavenging effect of Mn.},
doi = {10.1016/j.apcatb.2022.121424},
journal = {Applied Catalysis. B, Environmental},
number = NA,
volume = 312,
place = {United States},
year = {2022},
month = {4}
}

Works referenced in this record:

The Effect of Proton Conductivity of Fe–N–C–Based Cathode on PEM Fuel cell Performance
journal, April 2020

  • Reshetenko, Tatyana; Randolf, Günter; Odgaard, Madeleine
  • Journal of The Electrochemical Society, Vol. 167, Issue 8
  • DOI: 10.1149/1945-7111/ab8825

Fe–N–C Catalyst Graphitic Layer Structure and Fuel Cell Performance
journal, June 2017


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
  • DOI: 10.1149/2.1431910jes

One-dimensional Model of Oxygen Transport Impedance Accounting for Convection Perpendicular to the Electrode
journal, August 2012


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
  • DOI: 10.1038/ncomms13285

One-Dimensional Impedance of the Cathode Side of a PEM Fuel Cell: Exact Analytical Solution
journal, December 2014

  • Kulikovsky, A. A.
  • Journal of The Electrochemical Society, Vol. 162, Issue 3
  • DOI: 10.1149/2.0151503jes

Reflections on the history of electrochemical impedance spectroscopy
journal, January 2006


Impedance Spectroscopy Characterization of Oxygen Transport in Low– and High–Pt Loaded PEM Fuel Cells
journal, January 2017

  • Reshetenko, Tatyana; Kulikovsky, Andrei
  • Journal of The Electrochemical Society, Vol. 164, Issue 14
  • DOI: 10.1149/2.1131714jes

Review of System Integration and Control of Proton Exchange Membrane Fuel Cells
journal, May 2020


The Controllable Design of Catalyst Inks to Enhance PEMFC Performance: A Review
journal, November 2020


A Multi-Scale Dynamic Mechanistic Model for the Transient Analysis of PEFCs
journal, April 2007


A Fast Low-Current Model for Impedance of a PEM Fuel Cell Cathode at Low Air Stoichiometry
journal, January 2017

  • Kulikovsky, Andrei
  • Journal of The Electrochemical Society, Vol. 164, Issue 9
  • DOI: 10.1149/2.0561709jes

SiO2-Fe/N/C catalyst with enhanced mass transport in PEM fuel cells
journal, May 2020


Coupling High-Throughput Experiments and Regression Algorithms to Optimize PGM-Free ORR Electrocatalyst Synthesis
journal, August 2020

  • Karim, Mohammad Rezaul; Ferrandon, Magali; Medina, Samantha
  • ACS Applied Energy Materials, Vol. 3, Issue 9
  • DOI: 10.1021/acsaem.0c01466

Electrochemical Impedance Spectroscopy and its Applications
book, January 2002

  • Lasia, Andrzej; Conway, B. E.; Bockris, J. O'M.
  • Modern Aspects of Electrochemistry, p. 143-248
  • DOI: 10.1007/0-306-46916-2_2

Electrochemical impedance of the cathode catalyst layer in polymer electrolyte fuel cells
journal, October 1999


Platinum group metal-free catalysts boost cost competitiveness of fuel cell vehicles
journal, July 2019


AC impedance modelling study on porous electrodes of proton exchange membrane fuel cells using an agglomerate model
journal, November 2007


Analytical Impedance of Oxygen Transport in a PEM Fuel Cell Channel
journal, January 2019

  • Kulikovsky, Andrei
  • Journal of The Electrochemical Society, Vol. 166, Issue 4
  • DOI: 10.1149/2.0951904jes

PEM Fuel Cell Characterization by Means of the Physical Model for Impedance Spectra
journal, January 2015

  • Reshetenko, Tatyana; Kulikovsky, Andrei
  • Journal of The Electrochemical Society, Vol. 162, Issue 7
  • DOI: 10.1149/2.1141506jes

Investigation of mass transport in gas diffusion layer at the air cathode of a PEMFC
journal, October 2005


Investigation of Proton Transport in the Catalyst Layer of PEM Fuel Cells by Electrochemical Impedance Spectroscopy
journal, April 2010

  • Cimenti, Massimiliano; Bessarabov, Dmitri; Tam, Mickey
  • ECS Transactions, Vol. 28, Issue 23
  • DOI: 10.1149/1.3502346

Chemistry of Multitudinous Active Sites for Oxygen Reduction Reaction in Transition Metal–Nitrogen–Carbon Electrocatalysts
journal, November 2015

  • Artyushkova, Kateryna; Serov, Alexey; Rojas-Carbonell, Santiago
  • The Journal of Physical Chemistry C, Vol. 119, Issue 46
  • DOI: 10.1021/acs.jpcc.5b07653

Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells
journal, October 2018


A Steady-State Impedance Model for a PEMFC Cathode
journal, January 2004

  • Guo, Qingzhi; White, Ralph E.
  • Journal of The Electrochemical Society, Vol. 151, Issue 4
  • DOI: 10.1149/1.1648024

Analysis of the effect of catalyst layer thickness on the performance and durability of platinum group metal-free catalysts for polymer electrolyte membrane fuel cells
journal, January 2019

  • Baricci, Andrea; Bisello, Andrea; Serov, Alexey
  • Sustainable Energy & Fuels, Vol. 3, Issue 12
  • DOI: 10.1039/C9SE00252A

A Model for PEM Fuel Cell Impedance: Oxygen Flow in the Channel Triggers Spatial and Frequency Oscillations of the Local Impedance
journal, January 2015

  • Kulikovsky, Andrei; Shamardina, Olga
  • Journal of The Electrochemical Society, Vol. 162, Issue 9
  • DOI: 10.1149/2.0911509jes

Transition metal and nitrogen-doped mesoporous carbons as cathode catalysts for anion-exchange membrane fuel cells
journal, June 2022


On the Influence of Oxygen on the Degradation of Fe‐N‐C Catalysts
journal, January 2020

  • Kumar, Kavita; Dubau, Laetitia; Mermoux, Michel
  • Angewandte Chemie, Vol. 132, Issue 8
  • DOI: 10.1002/ange.201912451

Locally Resolved Electrochemical Impedance Spectroscopy in Channel and Land Areas of a Differential Polymer Electrolyte Fuel Cell
journal, January 2011

  • Schneider, I. A.; Bayer, M. H.; von Dahlen, S.
  • Journal of The Electrochemical Society, Vol. 158, Issue 3
  • DOI: 10.1149/1.3536498

Characterization of Polymer Electrolyte Fuel Cells Using AC Impedance Spectroscopy
journal, January 1996

  • Springer, T. E.
  • Journal of The Electrochemical Society, Vol. 143, Issue 2
  • DOI: 10.1149/1.1836485

Electron and proton conductivity of Fe-N-C cathodes for PEM fuel cells: A model-based electrochemical impedance spectroscopy measurement
journal, September 2020


Achievements, challenges and perspectives on cathode catalysts in proton exchange membrane fuel cells for transportation
journal, July 2019


PGM-Free Oxygen-Reduction Catalyst Development for Proton-Exchange Membrane Fuel Cells: Challenges, Solutions, and Promises
journal, January 2022


A pyridinic Fe-N4 macrocycle models the active sites in Fe/N-doped carbon electrocatalysts
journal, October 2020

  • Marshall-Roth, Travis; Libretto, Nicole J.; Wrobel, Alexandra T.
  • Nature Communications, Vol. 11, Issue 1
  • DOI: 10.1038/s41467-020-18969-6

Characterizing Complex Gas–Solid Interfaces with in Situ Spectroscopy: Oxygen Adsorption Behavior on Fe–N–C Catalysts
journal, July 2020

  • Dzara, Michael J.; Artyushkova, Kateryna; Sougrati, Moulay Tahar
  • The Journal of Physical Chemistry C, Vol. 124, Issue 30
  • DOI: 10.1021/acs.jpcc.0c05244

Impact of Inhomogeneous Catalyst Layer Properties on Impedance Spectra of Polymer Electrolyte Membrane Fuel Cells
journal, January 2015

  • Gerteisen, Dietmar
  • Journal of The Electrochemical Society, Vol. 162, Issue 14
  • DOI: 10.1149/2.0511514jes

US Department of Energy hydrogen and fuel cell technologies perspectives
journal, January 2020

  • Miller, Eric L.; Thompson, Simon T.; Randolph, Katie
  • MRS Bulletin, Vol. 45, Issue 1
  • DOI: 10.1557/mrs.2019.312

Use of a segmented cell for the combinatorial development of platinum group metal-free electrodes for polymer electrolyte fuel cells
journal, March 2020


On the Origin of High Frequency Impedance Feature in a PEM Fuel Cell
journal, January 2019

  • Reshetenko, Tatyana; Kulikovsky, Andrei
  • Journal of The Electrochemical Society, Vol. 166, Issue 15
  • DOI: 10.1149/2.1201915jes

Chemical vapour deposition of Fe–N–C oxygen reduction catalysts with full utilization of dense Fe–N4 sites
journal, June 2021


Transient Techniques for Investigating Mass-Transport Limitations in Gas Diffusion Electrodes
journal, January 2003

  • Jaouen, Frédéric; Lindbergh, Göran
  • Journal of The Electrochemical Society, Vol. 150, Issue 12
  • DOI: 10.1149/1.1624294

A Transient Fuel Cell Model to Simulate HTPEM Fuel Cell Impedance Spectra
conference, March 2012

  • Vang, Jakob Rabjerg; Andreasen, So̸ren Juhl; Kær, So̸ren Knudsen
  • ASME 2011 9th International Conference on Fuel Cell Science, Engineering and Technology collocated with ASME 2011 5th International Conference on Energy Sustainability
  • DOI: 10.1115/FuelCell2011-54880

Durability evaluation of a Fe–N–C catalyst in polymer electrolyte fuel cell environment via accelerated stress tests
journal, December 2020


Templated bi-metallic non-PGM catalysts for oxygen reduction
journal, October 2012


Commercial platinum group metal-free cathodic electrocatalysts for highly performed direct methanol fuel cell applications
journal, October 2019


Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst
journal, August 2017


Structure, composition, and chemical reactivity of carbon nanotubes by selective nitrogen doping
journal, July 2006