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

Title: Elucidating the Role of Ionomer in the Performance of Platinum Group Metal-free Catalyst Layer via in situ Electrochemical Diagnostics

Abstract

The ionomer content in platinum group metal (PGM)-free polymer electrolyte fuel cell (PEFC) cathode catalyst layer (CCL) plays an important role in the electrode gas transport properties, proton conductivity, and hence, membrane electrode assembly (MEA) performance. In this work, the ionomer content in the CCL is varied, influencing electrode microstructure by altering porosity, tortuosity, as well as ionomer distribution and coverage of the catalyst particles. A novel technique consisting of a H2 pump, combined with a Pt black sensor layer, is used to measure the bulk mass transport resistance of a series of PGM-free CCL prepared with different ionomer contents. The values for bulk electrode mass transport resistance are contrasted with electrode proton transport resistance in the cathode catalyst layer, establishing a clearly defined trade-off between two key performance limiting phenomena and identifying a need for novel PGM-free electrode fabrication strategies.

Authors:
 [1]; ORCiD logo [1];  [1];  [1]; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office
OSTI Identifier:
1665788
Report Number(s):
NREL/JA-5900-77218
Journal ID: ISSN 1945-7111; MainId:26164;UUID:837cb35f-c5d7-474d-b6c5-fdbb2ac09eed;MainAdminID:13747
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society (Online)
Additional Journal Information:
Journal Name: Journal of the Electrochemical Society (Online); Journal Volume: 167; Journal Issue: 4; Journal ID: ISSN 1945-7111
Publisher:
IOP Publishing
Country of Publication:
United States
Language:
English
Subject:
39 EE - Hydrogen and Fuel Cell Technologies (EE-3F); catalysts; cathodes; economic and social effects; platinum; polyelectrolytes; proton exchange membrane fuel cells; PEMFC

Citation Formats

Wang, Guanxiong, Osmieri, Luigi, Star, Andrew G., Pfeilsticker, Jason, and Neyerlin, Kenneth C. Elucidating the Role of Ionomer in the Performance of Platinum Group Metal-free Catalyst Layer via in situ Electrochemical Diagnostics. United States: N. p., 2020. Web. doi:10.1149/1945-7111/ab7aa1.
Wang, Guanxiong, Osmieri, Luigi, Star, Andrew G., Pfeilsticker, Jason, & Neyerlin, Kenneth C. Elucidating the Role of Ionomer in the Performance of Platinum Group Metal-free Catalyst Layer via in situ Electrochemical Diagnostics. United States. doi:10.1149/1945-7111/ab7aa1.
Wang, Guanxiong, Osmieri, Luigi, Star, Andrew G., Pfeilsticker, Jason, and Neyerlin, Kenneth C. Mon . "Elucidating the Role of Ionomer in the Performance of Platinum Group Metal-free Catalyst Layer via in situ Electrochemical Diagnostics". United States. doi:10.1149/1945-7111/ab7aa1. https://www.osti.gov/servlets/purl/1665788.
@article{osti_1665788,
title = {Elucidating the Role of Ionomer in the Performance of Platinum Group Metal-free Catalyst Layer via in situ Electrochemical Diagnostics},
author = {Wang, Guanxiong and Osmieri, Luigi and Star, Andrew G. and Pfeilsticker, Jason and Neyerlin, Kenneth C.},
abstractNote = {The ionomer content in platinum group metal (PGM)-free polymer electrolyte fuel cell (PEFC) cathode catalyst layer (CCL) plays an important role in the electrode gas transport properties, proton conductivity, and hence, membrane electrode assembly (MEA) performance. In this work, the ionomer content in the CCL is varied, influencing electrode microstructure by altering porosity, tortuosity, as well as ionomer distribution and coverage of the catalyst particles. A novel technique consisting of a H2 pump, combined with a Pt black sensor layer, is used to measure the bulk mass transport resistance of a series of PGM-free CCL prepared with different ionomer contents. The values for bulk electrode mass transport resistance are contrasted with electrode proton transport resistance in the cathode catalyst layer, establishing a clearly defined trade-off between two key performance limiting phenomena and identifying a need for novel PGM-free electrode fabrication strategies.},
doi = {10.1149/1945-7111/ab7aa1},
journal = {Journal of the Electrochemical Society (Online)},
number = 4,
volume = 167,
place = {United States},
year = {2020},
month = {3}
}

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

Save / Share:

Works referenced in this record:

Grid-connected hydrogen production via large-scale water electrolysis
journal, November 2019


PEFC catalyst layer: Recent advances in materials, microstructural characterization, and modeling
journal, October 2017


The Priority and Challenge of High-Power Performance of Low-Platinum Proton-Exchange Membrane Fuel Cells
journal, March 2016


A review on non-precious metal electrocatalysts for PEM fuel cells
journal, January 2011

  • Chen, Zhongwei; Higgins, Drew; Yu, Aiping
  • Energy & Environmental Science, Vol. 4, Issue 9
  • DOI: 10.1039/c0ee00558d

A study on the characteristics of the diffusion layer thickness and porosity of the PEMFC
journal, May 2004


Analysis of Oxygen-Transport Diffusion Resistance in Proton-Exchange-Membrane Fuel Cells
journal, January 2011

  • Nonoyama, Nobuaki; Okazaki, Shinobu; Weber, Adam Z.
  • Journal of The Electrochemical Society, Vol. 158, Issue 4
  • DOI: 10.1149/1.3546038

The use of different types of reduced graphene oxide in the preparation of Fe-N-C electrocatalysts: capacitive behavior and oxygen reduction reaction activity in alkaline medium
journal, July 2016

  • Osmieri, Luigi; Monteverde Videla, Alessandro H. A.; Specchia, Stefania
  • Journal of Solid State Electrochemistry, Vol. 20, Issue 12
  • DOI: 10.1007/s10008-016-3332-2

Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs
journal, March 2005

  • Gasteiger, Hubert A.; Kocha, Shyam S.; Sompalli, Bhaskar
  • Applied Catalysis B: Environmental, Vol. 56, Issue 1-2, p. 9-35
  • DOI: 10.1016/j.apcatb.2004.06.021

Understanding inks for porous-electrode formation
journal, January 2017

  • Hatzell, Kelsey B.; Dixit, Marm B.; Berlinger, Sarah A.
  • J. Mater. Chem. A, Vol. 5, Issue 39
  • DOI: 10.1039/C7TA07255D

Investigation of a polymer electrolyte membrane fuel cell catalyst layer with bidirectionally-graded composition
journal, December 2014


A Critical Review of Modeling Transport Phenomena in Polymer-Electrolyte Fuel Cells
journal, January 2014

  • Weber, Adam Z.; Borup, Rodney L.; Darling, Robert M.
  • Journal of The Electrochemical Society, Vol. 161, Issue 12
  • DOI: 10.1149/2.0751412jes

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


Gravure Coating for Roll-to-Roll Manufacturing of Proton-Exchange-Membrane Fuel Cell Catalyst Layers
journal, January 2018

  • Mauger, Scott A.; Neyerlin, K. C.; Yang-Neyerlin, Ami C.
  • Journal of The Electrochemical Society, Vol. 165, Issue 11
  • DOI: 10.1149/2.0091813jes

Agglomerates in Polymer Electrolyte Fuel Cell Electrodes: Part II. Transport Characterization
journal, January 2018

  • Cetinbas, Firat C.; Ahluwalia, Rajesh K.
  • Journal of The Electrochemical Society, Vol. 165, Issue 13
  • DOI: 10.1149/2.0301813jes

Dictating Pt-Based Electrocatalyst Performance in Polymer Electrolyte Fuel Cells, from Formulation to Application
journal, November 2019

  • Van Cleve, Tim; Khandavalli, Sunilkumar; Chowdhury, Anamika
  • ACS Applied Materials & Interfaces, Vol. 11, Issue 50
  • DOI: 10.1021/acsami.9b17614

Impact of Ultra-low Platinum loading on Mass Activity and Mass Transport in H2-Oxygen and H2-Air PEM Fuel Cells
journal, March 2014


Does CO poison Fe-based catalysts for ORR?
journal, May 2010


Advancements in rationally designed PGM-free fuel cell catalysts derived from metal–organic frameworks
journal, January 2017

  • Barkholtz, Heather M.; Liu, Di-Jia
  • Materials Horizons, Vol. 4, Issue 1
  • DOI: 10.1039/C6MH00344C

Ionic Conductivity of PEMFC Electrodes
journal, January 2003

  • Li, Guangchun; Pickup, Peter G.
  • Journal of The Electrochemical Society, Vol. 150, Issue 11
  • DOI: 10.1149/1.1611493

Nafion-based membrane electrode assemblies prepared from catalyst inks containing alcohol/water solvent mixtures
journal, September 2013


Recent Advances in Electrocatalysts for Oxygen Reduction Reaction
journal, February 2016


Measurement of Catalyst Layer Electrolyte Resistance in PEFCs Using Electrochemical Impedance Spectroscopy
journal, January 2005

  • Makharia, Rohit; Mathias, Mark F.; Baker, Daniel R.
  • Journal of The Electrochemical Society, Vol. 152, Issue 5
  • DOI: 10.1149/1.1888367

Highly Active Non-PGM Catalysts Prepared from Metal Organic Frameworks
journal, June 2015

  • Barkholtz, Heather; Chong, Lina; Kaiser, Zachary
  • Catalysts, Vol. 5, Issue 2
  • DOI: 10.3390/catal5020955

Measurement of Oxygen Transport Resistance in PEM Fuel Cells by Limiting Current Methods
journal, January 2009

  • Baker, Daniel R.; Caulk, David A.; Neyerlin, Kenneth C.
  • Journal of The Electrochemical Society, Vol. 156, Issue 9
  • DOI: 10.1149/1.3152226

Rheological Investigation on the Microstructure of Fuel Cell Catalyst Inks
journal, December 2018

  • Khandavalli, Sunilkumar; Park, Jae Hyung; Kariuki, Nancy N.
  • ACS Applied Materials & Interfaces, Vol. 10, Issue 50
  • DOI: 10.1021/acsami.8b15039

The Impact of Platinum Loading on Oxygen Transport Resistance
journal, January 2012

  • Greszler, Thomas A.; Caulk, David; Sinha, Puneet
  • Journal of The Electrochemical Society, Vol. 159, Issue 12
  • DOI: 10.1149/2.061212jes

Elucidating the Dynamic Nature of Fuel Cell Electrodes as a Function of Conditioning: An ex Situ Material Characterization and in Situ Electrochemical Diagnostic Study
journal, November 2019

  • Kabir, Sadia; Myers, Deborah J.; Kariuki, Nancy
  • ACS Applied Materials & Interfaces, Vol. 11, Issue 48
  • DOI: 10.1021/acsami.9b11365

Carbon materials for the electrochemical storage of energy in capacitors
journal, May 2001


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
  • DOI: 10.1002/adma.201806545

Electrochemical Capacitances of Well-Defined Carbon Surfaces
journal, October 2006

  • Kim, Taegon; Lim, Seongyop; Kwon, Kihyun
  • Langmuir, Vol. 22, Issue 22
  • DOI: 10.1021/la061380q

Nanostructured Nonprecious Metal Catalysts for Oxygen Reduction Reaction
journal, April 2013

  • Wu, Gang; Zelenay, Piotr
  • Accounts of Chemical Research, Vol. 46, Issue 8
  • DOI: 10.1021/ar400011z

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
  • DOI: 10.1021/acsami.6b08844

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


Fuel-Cell Catalyst-Layer Resistance via Hydrogen Limiting-Current Measurements
journal, January 2019

  • Schuler, Tobias; Chowdhury, Anamika; Freiberg, Anna T.
  • Journal of The Electrochemical Society, Vol. 166, Issue 7
  • DOI: 10.1149/2.0031907jes

Nonprecious Metal Catalysts for Oxygen Reduction in Heterogeneous Aqueous Systems
journal, December 2017


Performance of a Fe-N-C catalyst for the oxygen reduction reaction in direct methanol fuel cell: Cathode formulation optimization and short-term durability
journal, February 2017

  • Osmieri, Luigi; Escudero-Cid, Ricardo; Monteverde Videla, Alessandro H. A.
  • Applied Catalysis B: Environmental, Vol. 201
  • DOI: 10.1016/j.apcatb.2016.08.043

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
  • DOI: 10.1039/C6EE03005J

Recent advances in non-precious metal catalysis for oxygen-reduction reaction in polymer electrolyte fuelcells
journal, January 2011

  • Jaouen, Frédéric; Proietti, Eric; Lefèvre, Michel
  • Energy Environ. Sci., Vol. 4, Issue 1, p. 114-130
  • DOI: 10.1039/C0EE00011F

Performance of Polymer Electrolyte Fuel Cell Electrodes with Atomically Dispersed (AD) Fe-C-N ORR Catalyst
journal, January 2019

  • Ahluwalia, R. K.; Wang, X.; Osmieri, L.
  • Journal of The Electrochemical Society, Vol. 166, Issue 14
  • DOI: 10.1149/2.0851914jes

Investigating fuel-cell transport limitations using hydrogen limiting current
journal, May 2017


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
  • DOI: 10.1126/science.1170051

Effect of carbon black support corrosion on the durability of Pt/C catalyst
journal, September 2007


Ink Solvent Dependence of the Ionomer Distribution in the Catalyst Layer of a PEMFC
journal, January 2018

  • Orfanidi, Alin; Rheinländer, Philipp J.; Schulte, Nicole
  • Journal of The Electrochemical Society, Vol. 165, Issue 14
  • DOI: 10.1149/2.1251814jes

Influence of Equivalent Weight of Ionomer on Local Oxygen Transport Resistance in Cathode Catalyst Layers
journal, January 2013

  • Ono, Yoshitaka; Ohma, Atsushi; Shinohara, Kazuhiko
  • Journal of The Electrochemical Society, Vol. 160, Issue 8
  • DOI: 10.1149/2.040308jes

Cathode Catalyst Utilization for the ORR in a PEMFC
journal, January 2007

  • Neyerlin, K. C.; Gu, Wenbin; Jorne, Jacob
  • Journal of The Electrochemical Society, Vol. 154, Issue 2
  • DOI: 10.1149/1.2400626

Nano-electrocatalyst materials for low temperature fuel cells: A review
journal, April 2015


Cost and well-to-wheel implications of the vehicle fleet CO2 emission regulation in the European Union
journal, May 2014

  • Thiel, Christian; Schmidt, Johannes; Van Zyl, Arnold
  • Transportation Research Part A: Policy and Practice, Vol. 63
  • DOI: 10.1016/j.tra.2014.02.018

Experimental Observation of Redox-Induced Fe–N Switching Behavior as a Determinant Role for Oxygen Reduction Activity
journal, October 2015