Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

Correlating the Morphological Changes to Electrochemical Performance During Carbon Corrosion in Polymer Electrolyte Fuel Cells

Journal Article · · Journal of Materials Chemistry A
DOI:https://doi.org/10.1039/D2TA02666J· OSTI ID:1876022

A mechanistic understanding of carbon corrosion in polymer electrolyte fuel cells (PEFCs) is required to design durable catalyst layers. Uncontrolled startup and shutdown of PEFCs cause electrochemical oxidation of carbon, which leads to several degradation phenomena, such as loss in electrochemical surface area (ECSA), pore structure collapse or increase in mass transport resistance. In this study, the chronology of morphological changes in the cathode catalyst layer due to carbon corrosion was identified and correlated with electrochemical performance degradation. PEFCs were subjected to the Department of Energy carbon corrosion accelerated stress test (AST) protocol. The study revealed two phases: in the initial phase (~500 AST cycles), amorphous carbon in contact with Pt nanoparticles oxidized fast. Rapid carbon loss and catalyst layer thinning occurred, but pore structure did not change significantly. Pt nanoparticles detached from the support and ECSA decreased drastically. In the second phase (~1500 AST cycles), carbon corrosion slowed down, but severe pore structure collapse was observed. Porosity and pore connectivity within the cathode catalyst layer decreased considerably. Electrochemical diagnostics corroborated this finding by showing significantly higher O2 mass transport resistance. Lastly, no significant change was observed in the concentration of oxides on the carbon surface after AST. But overall water management in the cathode catalyst layer deteriorated as the pore structure collapsed. This study provides an in-depth understanding of morphological changes during PEFC carbon corrosion AST protocol and motivates novel material design strategies to enable durable PEFCs.

Research Organization:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
DOE Contract Number:
AC36-08GO28308
OSTI ID:
1876022
Report Number(s):
NREL/JA-5900-83412; MainId:84185; UUID:d4fb4948-deb3-427d-9bd5-ecf22144325a; MainAdminID:64836
Journal Information:
Journal of Materials Chemistry A, Journal Name: Journal of Materials Chemistry A Journal Issue: 23 Vol. 10
Country of Publication:
United States
Language:
English

References (55)

Mapping of Heterogeneous Catalyst Degradation in Polymer Electrolyte Fuel Cells journal June 2020
Physical Theory of Platinum Nanoparticle Dissolution in Polymer Electrolyte Fuel Cells journal March 2010
Diagnosing Degradation within PEM Fuel Cell Catalyst Layers Using Electrochemical Impedance Spectroscopy journal January 2012
Scientific Aspects of Polymer Electrolyte Fuel Cell Durability and Degradation journal October 2007
A Reverse-Current Decay Mechanism for Fuel Cells journal January 2005
Measurement of Oxygen Transport Resistance in PEM Fuel Cells by Limiting Current Methods journal January 2009
Crystallite growth of platinum dispersed on graphitized carbon black journal November 1974
Theoretical analysis of electrochemical surface-area loss in supported nanoparticle catalysts journal January 2014
Real surface area measurements in electrochemistry journal January 1991
Analysis of Oxygen-Transport Diffusion Resistance in Proton-Exchange-Membrane Fuel Cells journal January 2011
In situ mapping of potential transients during start-up and shut-down of a polymer electrolyte membrane fuel cell journal December 2014
Kinetic Model of Platinum Dissolution in PEMFCs journal January 2003
The Priority and Challenge of High-Power Performance of Low-Platinum Proton-Exchange Membrane Fuel Cells journal March 2016
Mitigated Start-Up of PEMFC in Real Automotive Conditions: Local Experimental Investigation and Development of a New Accelerated Stress Test Protocol journal April 2021
Measurement of Catalyst Layer Electrolyte Resistance in PEFCs Using Electrochemical Impedance Spectroscopy journal January 2005
Absolute permeability and Knudsen diffusivity measurements in PEMFC gas diffusion layers and micro porous layers journal May 2012
Kinetic model of the electrochemical oxidation of graphitic carbon in acidic environments journal January 2009
Determination of Catalyst Unique Parameters for the Oxygen Reduction Reaction in a PEMFC journal January 2006
Accelerated Testing of Carbon Corrosion and Membrane Degradation in PEM Fuel Cells journal March 2013
TauFactor: An open-source application for calculating tortuosity factors from tomographic data journal January 2016
PEM Fuel Cell Start-Up/Shut-Down Losses vs Relative Humidity: The Impact of Water in the Electrode Layer on Carbon Corrosion journal January 2018
Effect of Carbon Corrosion on Wettability of PEM Fuel Cell Electrodes journal January 2019
Ionomer migration within PEMFC catalyst layers induced by humidity changes journal December 2019
Measurements of Pore Size Distribution, Porosity, Effective Oxygen Diffusivity, and Tortuosity of PEM Fuel Cell Electrodes journal June 2012
The effect of platinum on carbon corrosion behavior in polymer electrolyte fuel cells journal September 2011
Probing Heterogeneous Degradation of Catalyst in PEM Fuel Cells under Realistic Automotive Conditions with Multi‐Modal Techniques journal July 2021
Impact of Corrosion Conditions on Carbon Paper Electrode Morphology and the Performance of a Vanadium Redox Flow Battery journal January 2019
Electrochemical impedance of the cathode catalyst layer in polymer electrolyte fuel cells journal October 1999
Influence of the Gas Diffusion Layer Compression on the Oxygen Transport in PEM Fuel Cells at High Water Saturation Levels journal January 2017
Carbon Corrosion in Proton-Exchange Membrane Fuel Cells: Effect of the Carbon Structure, the Degradation Protocol, and the Gas Atmosphere journal March 2015
Identical-location TEM investigations of Pt/C electrocatalyst degradation at elevated temperatures journal November 2011
Development of a Titanium Dioxide-Supported Platinum Catalyst with Ultrahigh Stability for Polymer Electrolyte Membrane Fuel Cell Applications journal October 2009
Study on the processes of start-up and shutdown in proton exchange membrane fuel cells journal April 2009
Carbon Corrosion in PEM Fuel Cells and the Development of Accelerated Stress Tests journal January 2018
PEM Fuel Cell Start-up/Shut-down Losses vs Temperature for Non-Graphitized and Graphitized Cathode Carbon Supports journal December 2016
Modeling and Investigation of Carbon Loss on the Cathode Electrode during PEMFC Operation journal January 2010
Determination of Electrode Sheet Resistance in Cathode Catalyst Layer by AC Impedance conference January 2007
Cathode Loading Impact on Voltage Cycling Induced PEMFC Degradation: A Voltage Loss Analysis journal January 2018
Gas-diffusion-layer structural properties under compression via X-ray tomography journal October 2016
Voltammetry of Quinones in Unbuffered Aqueous Solution: Reassessing the Roles of Proton Transfer and Hydrogen Bonding in the Aqueous Electrochemistry of Quinones journal October 2007
Fiji: an open-source platform for biological-image analysis journal June 2012
A review of automotive proton exchange membrane fuel cell degradation under start-stop operating condition journal August 2018
Carbon support oxidation in PEM fuel cell cathodes journal February 2008
FIB-SEM Tomography Connects Microstructure to Corrosion-Induced Performance Loss in PEMFC Cathodes journal January 2017
Nano-morphology of a polymer electrolyte fuel cell catalyst layer—imaging, reconstruction and analysis journal May 2011
Catalyst Durability in PEM Fuel Cells with Low Platinum Loading journal January 2012
Advanced catalyst supports for PEM fuel cell cathodes journal November 2016
Systems Strategies to Mitigate Carbon Corrosion in Fuel Cells conference January 2006
OpenPNM: A Pore Network Modeling Package journal July 2016
Effect of Catalyst and Catalyst Layer Composition on Catalyst Support Durability journal April 2021
On the Micro-, Meso-, and Macroporous Structures of Polymer Electrolyte Membrane Fuel Cell Catalyst Layers journal January 2010
Mathematical Model of Platinum Movement in PEM Fuel Cells journal January 2005
Impact of Carbon Support Corrosion on Performance Losses in Polymer Electrolyte Membrane Fuel Cells journal January 2019
Electrochemical impedance analysis with transmission line model for accelerated carbon corrosion in polymer electrolyte membrane fuel cells journal August 2018
Analysis of Catalyst Layer Microstructures: From Imaging to Performance journal July 2016