Effects of Porous Carbon Morphology, Agglomerate Structure and Relative Humidity on Local O2 Transport Resistance

Cetinbas, Firat C.; Ahluwalia, Rajesh K.; Kariuki, Nancy N.; De Andrade, Vincent; Myers, Deborah J.

doi:10.1149/2.0082001JES

Title: Effects of Porous Carbon Morphology, Agglomerate Structure and Relative Humidity on Local O₂ Transport Resistance

Journal Article · Mon Sep 23 00:00:00 EDT 2019 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/2.0082001JES· OSTI ID:1570441

Cetinbas, Firat C.; Ahluwalia, Rajesh K.; Kariuki, Nancy N.; De Andrade, Vincent; Myers, Deborah J.

The morphology and ionomer distribution in a polymer electrolyte membrane fuel cell (PEMFC) cathode electrode are quantified with nano-scale resolution X-ray computed tomography (nano-CT). Using the nano-CT data, different shapes, sizes and compositions of agglomerates are extracted. Statistical information from multiple techniques, including transmission electron microscopy (TEM), ultra-small angle X-ray scattering (USAXS), and Brunauer-Emmett-Teller (BET) gas adsorption porosimetry are combined to reconstruct the high surface-area porous carbon (HSC) support, exterior (on the surface of carbon) and interior (inside carbon pores) catalysts, ionomer, and primary pores in the extracted agglomerates. Application of capillary condensation theory to the reconstructed agglomerate structure is shown to accurately represent the experimentally-observed relative humidity (RH) dependence of the electrochemically-active surface area (ECA). Direct numerical simulations show that the high local O₂ transport resistance (R_O2) under dry conditions is mainly associated with the reduced ECA. We demonstrate that the agglomerate shape and size affect R_O2 only if the primary pores are poorly accessible (i.e., capillary-condensed water filled primary pores). We also evaluate the effect of transport to the interior catalyst particles on R_O2.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE) - Office of Fuel Cell Technologies (FCTO)

DOE Contract Number:: AC02-06CH11357

OSTI ID:: 1570441

Journal Information:: Journal of the Electrochemical Society, Vol. 167, Issue 1; ISSN 0013-4651

Publisher:: The Electrochemical Society

Country of Publication:: United States

Language:: English

References (41)

Carbon supports for low-temperature fuel cell catalysts Antolini, Ermete Applied Catalysis B: Environmental, Vol. 88, Issue 1-2 https://doi.org/10.1016/j.apcatb.2008.09.030	journal	April 2009
3D Analysis of Fuel Cell Electrocatalyst Degradation on Alternate Carbon Supports Sneed, Brian T.; Cullen, David A.; Reeves, Kimberly S. ACS Applied Materials & Interfaces, Vol. 9, Issue 35 https://doi.org/10.1021/acsami.7b09716	journal	August 2017
An improved two-dimensional agglomerate cathode model to study the influence of catalyst layer structural parameters Sun, Wei; Peppley, Brant A.; Karan, Kunal Electrochimica Acta, Vol. 50, Issue 16-17 https://doi.org/10.1016/j.electacta.2004.12.009	journal	May 2005
The Priority and Challenge of High-Power Performance of Low-Platinum Proton-Exchange Membrane Fuel Cells Kongkanand, Anusorn; Mathias, Mark F. The Journal of Physical Chemistry Letters, Vol. 7, Issue 7 https://doi.org/10.1021/acs.jpclett.6b00216	journal	March 2016
Impact of Platinum Loading and Catalyst Layer Structure on PEMFC Performance Owejan, Jon P.; Owejan, Jeanette E.; Gu, Wenbin Journal of The Electrochemical Society, Vol. 160, Issue 8 https://doi.org/10.1149/2.072308jes	journal	January 2013
Electrocatalysis on Bimetallic Surfaces: Modifying Catalytic Reactivity for Oxygen Reduction by Voltammetric Surface Dealloying Koh, Shirlaine; Strasser, Peter Journal of the American Chemical Society, Vol. 129, Issue 42 https://doi.org/10.1021/ja0742784	journal	October 2007
A Modified Agglomerate Model with Discrete Catalyst Particles for the PEM Fuel Cell Catalyst Layer Cetinbas, Firat C.; Advani, Suresh G.; Prasad, Ajay K. Journal of The Electrochemical Society, Vol. 160, Issue 8 https://doi.org/10.1149/2.017308jes	journal	January 2013
Effects of carbon supports on Pt distribution, ionomer coverage and cathode performance for polymer electrolyte fuel cells Park, Young-Chul; Tokiwa, Haruki; Kakinuma, Katsuyoshi Journal of Power Sources, Vol. 315 https://doi.org/10.1016/j.jpowsour.2016.02.091	journal	May 2016
Gas transport inside and outside carbon supports of catalyst layers for PEM fuel cells Iden, Hiroshi; Mashio, Tetsuya; Ohma, Atsushi Journal of Electroanalytical Chemistry, Vol. 708 https://doi.org/10.1016/j.jelechem.2013.09.011	journal	November 2013
Analysis of Oxygen-Transport Diffusion Resistance in Proton-Exchange-Membrane Fuel Cells Nonoyama, Nobuaki; Okazaki, Shinobu; Weber, Adam Z. Journal of The Electrochemical Society, Vol. 158, Issue 4 https://doi.org/10.1149/1.3546038	journal	January 2011
Boosting Fuel Cell Performance with Accessible Carbon Mesopores Yarlagadda, Venkata; Carpenter, Michael K.; Moylan, Thomas E. ACS Energy Letters, Vol. 3, Issue 3 https://doi.org/10.1021/acsenergylett.8b00186	journal	February 2018
Sensitivity of PEFC Models to Cathode Layer Microstructure Jain, Parag; Biegler, Lorenz T.; Jhon, Myung S. Journal of The Electrochemical Society, Vol. 157, Issue 8 https://doi.org/10.1149/1.3454725	journal	January 2010
Proton Conduction and Oxygen Diffusion in Ultra-Thin Nafion Films in PEM Fuel Cell: How Thin? Chen, Darcy; Kongkanand, Anusorn; Jorne, Jacob Journal of The Electrochemical Society, Vol. 166, Issue 2 https://doi.org/10.1149/2.0101902jes	journal	January 2019
Three-Dimensional Spatial Distributions of Pt Catalyst Nanoparticles on Carbon Substrates in Polymer Electrolyte Fuel Cells Ito, Toshihiko; Matsuwaki, Ukyo; Otsuka, Yuji Electrochemistry, Vol. 79, Issue 5 https://doi.org/10.5796/electrochemistry.79.374	journal	January 2011
Achieving High-Power PEM Fuel Cell Performance with an Ultralow-Pt-Content Core–Shell Catalyst Kongkanand, Anusorn; Subramanian, Nalini P.; Yu, Yingchao ACS Catalysis, Vol. 6, Issue 3 https://doi.org/10.1021/acscatal.5b02819	journal	February 2016
The Impact of Platinum Loading on Oxygen Transport Resistance Greszler, Thomas A.; Caulk, David; Sinha, Puneet Journal of The Electrochemical Society, Vol. 159, Issue 12 https://doi.org/10.1149/2.061212jes	journal	January 2012
Adsorption of Water by Carbon ¹ Pierce, Conway; Smith, R. Nelson; Wiley, J. W. Journal of the American Chemical Society, Vol. 73, Issue 10 https://doi.org/10.1021/ja01154a018	journal	October 1951
Effects of an agglomerate size distribution on the PEFC agglomerate model Epting, William K.; Litster, Shawn International Journal of Hydrogen Energy, Vol. 37, Issue 10 https://doi.org/10.1016/j.ijhydene.2012.02.099	journal	May 2012
Dealloyed Core-Shell Fuel Cell Electrocatalysts Strasser, Peter Reviews in Chemical Engineering, Vol. 25, Issue 4 https://doi.org/10.1515/REVCE.2009.25.4.255	journal	January 2009
Analysis of proton exchange membrane fuel cell catalyst layers for reduction of platinum loading at Nissan Ohma, Atsushi; Mashio, Tetsuya; Sato, Kazuyuki Electrochimica Acta, Vol. 56, Issue 28 https://doi.org/10.1016/j.electacta.2011.04.058	journal	December 2011
(Plenary) Electrochemical Diagnostics and Modeling in Developing the PEMFC Cathode Kongkanand, A.; Yarlagadda, V.; Garrick, T. R. ECS Transactions, Vol. 75, Issue 14 https://doi.org/10.1149/07514.0025ecst	journal	August 2016
Microstructural Analysis and Transport Resistances of Low-Platinum-Loaded PEFC Electrodes Cetinbas, Firat C.; Wang, Xiaohua; Ahluwalia, Rajesh K. Journal of The Electrochemical Society, Vol. 164, Issue 14 https://doi.org/10.1149/2.1111714jes	journal	January 2017
Fiji: an open-source platform for biological-image analysis Schindelin, Johannes; Arganda-Carreras, Ignacio; Frise, Erwin Nature Methods, Vol. 9, Issue 7 https://doi.org/10.1038/nmeth.2019	journal	June 2012
Effects of catalyst agglomerate shape in polymer electrolyte fuel cells investigated by a multi-scale modelling framework Ismail, M. S.; Ingham, D. B.; Ma, L. Energy, Vol. 122 https://doi.org/10.1016/j.energy.2017.01.092	journal	March 2017
Relationship among Microstructure, Ionomer Property and Proton Transport in Pseudo Catalyst Layers Iden, Hiroshi; Sato, Kazuyuki; Ohma, Atsushi Journal of The Electrochemical Society, Vol. 158, Issue 8 https://doi.org/10.1149/1.3598141	journal	January 2011
The impact of the morphology of the carbon support on the activity and stability of nanoparticle fuel cell catalysts Tuaev, Xenia; Rudi, Stefan; Strasser, Peter Catalysis Science & Technology, Vol. 6, Issue 23 https://doi.org/10.1039/C6CY01679K	journal	January 2016
Resolving Electrode Morphology’s Impact on Platinum Group Metal-Free Cathode Performance Using Nano-CT of 3D Hierarchical Pore and Ionomer Distribution Komini Babu, Siddharth; Chung, Hoon T.; Zelenay, Piotr ACS Applied Materials & Interfaces, Vol. 8, Issue 48 https://doi.org/10.1021/acsami.6b08844	journal	November 2016
An Improved Agglomerate Model for the PEM Catalyst Layer with Accurate Effective Surface Area Calculation Based on the Sphere-Packing Approach Cetinbas, Firat C.; Advani, Suresh G.; Prasad, Ajay K. Journal of The Electrochemical Society, Vol. 161, Issue 6 https://doi.org/10.1149/2.116406jes	journal	January 2014
Efficient Management of Parallelism in Object-Oriented Numerical Software Libraries Balay, Satish; Gropp, William D.; McInnes, Lois Curfman Modern Software Tools for Scientific Computing https://doi.org/10.1007/978-1-4612-1986-6_8	book	January 1997
Agglomerates in Polymer Electrolyte Fuel Cell Electrodes: Part II. Transport Characterization Cetinbas, Firat C.; Ahluwalia, Rajesh K. Journal of The Electrochemical Society, Vol. 165, Issue 13 https://doi.org/10.1149/2.0301813jes	journal	January 2018
3-D Microstructure Analysis of Fuel Cell Materials: Spatial Distributions of Tortuosity, Void Size and Diffusivity Çeçen, A.; Wargo, E. A.; Hanna, A. C. Journal of The Electrochemical Society, Vol. 159, Issue 3 https://doi.org/10.1149/2.068203jes	journal	January 2012
Modelling the PEM fuel cell cathode Broka, K.; Ekdunge, P. Journal of Applied Electrochemistry, Vol. 27, Issue 3, p. 281-289 https://doi.org/10.1023/A:1018476612810	journal	March 1997
Three dimensional proton exchange membrane fuel cell cathode model using a modified agglomerate approach based on discrete catalyst particles Cetinbas, Firat C.; Advani, Suresh G.; Prasad, Ajay K. Journal of Power Sources, Vol. 250 https://doi.org/10.1016/j.jpowsour.2013.10.138	journal	March 2014
Editors' Choice—Connecting Fuel Cell Catalyst Nanostructure and Accessibility Using Quantitative Cryo-STEM Tomography Padgett, Elliot; Andrejevic, Nina; Liu, Zhongyi Journal of The Electrochemical Society, Vol. 165, Issue 3 https://doi.org/10.1149/2.0541803jes	journal	January 2018
Hybrid approach combining multiple characterization techniques and simulations for microstructural analysis of proton exchange membrane fuel cell electrodes Cetinbas, Firat C.; Ahluwalia, Rajesh K.; Kariuki, Nancy Journal of Power Sources, Vol. 344 https://doi.org/10.1016/j.jpowsour.2017.01.104	journal	March 2017
Gas Permeation in SPE Method Ogumi, Z. Journal of The Electrochemical Society, Vol. 131, Issue 4 https://doi.org/10.1149/1.2115696	journal	January 1984
Characterizing Electrolyte and Platinum Interface in PEM Fuel Cells Using CO Displacement Garrick, Taylor R.; Moylan, Thomas E.; Yarlagadda, Venkata Journal of The Electrochemical Society, Vol. 164, Issue 2 https://doi.org/10.1149/2.0551702jes	journal	December 2016
Relative Humidity Dependence of Pt Utilization in Polymer Electrolyte Fuel Cell Electrodes: Effects of Electrode Thickness, Ionomer-to-Carbon Ratio, Ionomer Equivalent Weight, and Carbon Support Shinozaki, Kazuma; Yamada, Haruhiko; Morimoto, Yu Journal of The Electrochemical Society, Vol. 158, Issue 5 https://doi.org/10.1149/1.3556906	journal	January 2011
On the Micro-, Meso-, and Macroporous Structures of Polymer Electrolyte Membrane Fuel Cell Catalyst Layers Soboleva, Tatyana; Zhao, Xinsheng; Malek, Kourosh ACS Applied Materials & Interfaces, Vol. 2, Issue 2 https://doi.org/10.1021/am900600y	journal	January 2010
Integration of TomoPy and the ASTRA toolbox for advanced processing and reconstruction of tomographic synchrotron data Pelt, Daniël M.; Gürsoy, Dogˇa; Palenstijn, Willem Jan Journal of Synchrotron Radiation, Vol. 23, Issue 3 https://doi.org/10.1107/S1600577516005658	journal	April 2016
Agglomerates in Polymer Electrolyte Fuel Cell Electrodes: Part I. Structural Characterization Cetinbas, Firat C.; Ahluwalia, Rajesh K.; Kariuki, Nancy N. Journal of The Electrochemical Society, Vol. 165, Issue 13 https://doi.org/10.1149/2.0571813jes	journal	January 2018

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local O2 transport resistance

Title: Effects of Porous Carbon Morphology, Agglomerate Structure and Relative Humidity on Local O2 Transport Resistance

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Title: Effects of Porous Carbon Morphology, Agglomerate Structure and Relative Humidity on Local O₂ Transport Resistance