Unraveling the core of fuel cell performance: engineering the ionomer/catalyst interface

Li, Chenzhao; Yu, Kang; Bird, Ashley; Guo, Fei; Ilavsky, Jan; Liu, Yadong; Cullen, David A; Kusoglu, Ahmet; Weber, Adam Z; Ferreira, Paulo J; Xie, Jian

doi:10.1039/d2ee03553g

Unraveling the core of fuel cell performance: engineering the ionomer/catalyst interface

Journal Article · Thu May 11 00:00:00 EDT 2023 · Energy & Environmental Science

DOI:https://doi.org/10.1039/d2ee03553g· OSTI ID:2376889

Li, Chenzhao ^[1]; Yu, Kang ^[2]; ^[3]; Guo, Fei ^[4]; Ilavsky, Jan ^[5]; Liu, Yadong ^[6]; Cullen, David A ^[7]; Kusoglu, Ahmet ^[8]; Weber, Adam Z ^[8]; Ferreira, Paulo J ^[9]; Xie, Jian ^[6]

Indiana Univ.-Purdue Univ. Indianapolis (IUPUI), Indianapolis, IN (United States); Purdue Univ., West Lafayette, IN (United States)
Univ. of Texas, Austin, TX (United States); International Iberian Nanotechnology Laboratory, Braga (Portugal)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Energy Technologies Area; University of California, Berkeley, CA (United States)
Univ. of California, Davis, CA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)
Indiana Univ.-Purdue Univ. Indianapolis (IUPUI), Indianapolis, IN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Energy Technologies Area
Univ. of Texas, Austin, TX (United States); International Iberian Nanotechnology Laboratory, Braga (Portugal); Univ. of Lisbon (Portugal)

The biggest obstacle to the widespread implementation of polymer electrolyte membrane fuel cells (PEMFCs) is their cost, primarily due to the use of platinum catalysts. The high intrinsic catalyst activity exhibited on a rotating disk electrode (RDE) is rarely realized in a membrane electrode assembly (MEA), which is a long-standing challenge for PEMFCs and a cause of low catalyst utilization. To translate the high RDE performance of a catalyst into a MEA, the design of an ideal ionomer/catalyst interface is proposed: a thin, conformal ionomer film covers the maximum surface of a Pt nanoparticle and thus simultaneously maximizes catalyst utilization, (i.e., high mass activity and electrochemically active surface area) and O₂ diffusion rate (i.e., high current density performance) without compromising proton conduction. Building such an interface is a long-standing challenge due to the lack of interaction between the ionomer and catalyst particles, resulting in large ionomer agglomerates and inhomogeneous ionomer coverage over the catalyst nanoparticle, with consequent poor fuel cell performance. In this work, this ionomer/catalyst interface has been engineered, utilizing the electrostatic attraction between positively charged catalyst and negatively charged ionomer particles in a catalyst ink and preserved in a solid catalyst layer. As a result, this interface leads to previously unachieved proton exchange membrane fuel cell performance in terms of both catalyst utilization (75% vs. 45%) and peak/rated power density (i.e., 1.430/0.930 W cm^-2, H₂/air, cathode Pt loading: 0.1 mgPt cm^-2) for pure Pt catalysts, even better than those of Pt alloy catalysts. This work demonstrates the formation of an interface in the liquid phase (using ultra-small-angle X-ray scattering in combination with cryo-TEM, isothermal–titration–calorimetry) and the preservation of the interface in the solid catalyst layer (using TEM) and estimates the effective coverage and thickness of the ionomer film (using limiting current density, RDE and fuel cell performance).

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Hydrogen Fuel Cell Technologies Office (HFTO); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357

OSTI ID:: 2376889

Alternate ID(s):: OSTI ID: 2404850
OSTI ID: 1983720

Journal Information:: Energy & Environmental Science, Journal Name: Energy & Environmental Science Journal Issue: 7 Vol. 16; ISSN 1754-5692

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (49)

PGM‐Free Cathode Catalysts for PEM Fuel Cells: A Mini‐Review on Stability Challenges Shao, Yuyan; Dodelet, Jean‐Pol; Wu, Gang Advanced Materials, Vol. 31, Issue 31 https://doi.org/10.1002/adma.201807615	journal	December 2018
Tungsten‐Doped L1 ₀ ‐PtCo Ultrasmall Nanoparticles as a High‐Performance Fuel Cell Cathode Liang, Jiashun; Li, Na; Zhao, Zhonglong Angewandte Chemie International Edition, Vol. 58, Issue 43 https://doi.org/10.1002/anie.201908824	journal	October 2019
Automotive Li-Ion Batteries: Current Status and Future Perspectives Ding, Yuanli; Cano, Zachary P.; Yu, Aiping Electrochemical Energy Reviews, Vol. 2, Issue 1 https://doi.org/10.1007/s41918-018-0022-z	journal	January 2019
A comprehensive picture of the electrical phenomena in carbon black–polymer composites Balberg, I. Carbon, Vol. 40, Issue 2 https://doi.org/10.1016/S0008-6223(01)00164-6	journal	February 2002
Structural evolution of water swollen perfluorosulfonated ionomers from dry membrane to solution Gebel, G. Polymer, Vol. 41, Issue 15 https://doi.org/10.1016/S0032-3861(99)00770-3	journal	July 2000
Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs Gasteiger, Hubert A.; Kocha, Shyam S.; Sompalli, Bhaskar Applied Catalysis B: Environmental, Vol. 56, Issue 1-2, p. 9-35 https://doi.org/10.1016/j.apcatb.2004.06.021	journal	March 2005
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
Enhanced Pt/C catalyst stability using p-benzensulfonic acid functionalized carbon blacks as catalyst supports Xu, Fan; Wang, Mei-xian; Sun, Lili Electrochimica Acta, Vol. 94 https://doi.org/10.1016/j.electacta.2013.01.097	journal	April 2013
Water sorption on coals Charrière, Delphine; Behra, Philippe Journal of Colloid and Interface Science, Vol. 344, Issue 2 https://doi.org/10.1016/j.jcis.2009.11.064	journal	April 2010
Towards the understanding of transport limitations in a proton-exchange membrane fuel cell catalyst layer: Performing agglomerate scale direct numerical simulations on electron-microscopy-based geometries Barreiros Salvado, M.; Schott, P.; Guétaz, L. Journal of Power Sources, Vol. 482 https://doi.org/10.1016/j.jpowsour.2020.228893	journal	January 2021
Benchmarking proton exchange membrane fuel cell cathode catalyst at high current density: A comparison between the rotating disk electrode, the gas diffusion electrode and differential cell Riasse, Raphaël; Lafforgue, Clémence; Vandenberghe, Florent Journal of Power Sources, Vol. 556 https://doi.org/10.1016/j.jpowsour.2022.232491	journal	February 2023
Equilibrium and dynamic vapour water sorption properties of biochar derived from apple wood Popescu, Carmen-Mihaela; Hill, Callum A. S.; Anthony, Rosie Polymer Degradation and Stability, Vol. 111 https://doi.org/10.1016/j.polymdegradstab.2014.10.014	journal	January 2015
Inherent Acidity of Perfluorosulfonic Acid Ionomer Dispersions and Implications for Ink Aggregation Berlinger, Sarah A.; McCloskey, Bryan D.; Weber, Adam Z. The Journal of Physical Chemistry B, Vol. 122, Issue 31 https://doi.org/10.1021/acs.jpcb.8b06493	journal	July 2018
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
Simple and Reliable Method for Studying the Adsorption Behavior of Aquivion Ionomers on Carbon Black Surfaces Thoma, Martin; Lin, Wei; Hoffmann, Eva Langmuir, Vol. 34, Issue 41 https://doi.org/10.1021/acs.langmuir.8b02726	journal	September 2018
Investigation of the Interaction between Nafion Ionomer and Surface Functionalized Carbon Black Using Both Ultrasmall Angle X-ray Scattering and Cryo-TEM Yang, Fan; Xin, Le; Uzunoglu, Aytekin ACS Applied Materials & Interfaces, Vol. 9, Issue 7 https://doi.org/10.1021/acsami.6b12949	journal	February 2017
Elucidating the Dynamic Nature of Fuel Cell Electrodes as a Function of Conditioning: An ex Situ Material Characterization and in Situ Electrochemical Diagnostic Study Kabir, Sadia; Myers, Deborah J.; Kariuki, Nancy ACS Applied Materials & Interfaces, Vol. 11, Issue 48 https://doi.org/10.1021/acsami.9b11365	journal	November 2019
High-Performance Nitrogen-Doped Intermetallic PtNi Catalyst for the Oxygen Reduction Reaction Zhao, Xueru; Xi, Cong; Zhang, Rui ACS Catalysis, Vol. 10, Issue 18 https://doi.org/10.1021/acscatal.0c03036	journal	August 2020
Understanding Pt Nanoparticle Anchoring on Graphene Supports through Surface Functionalization Xin, Le; Yang, Fan; Rasouli, Somaye ACS Catalysis, Vol. 6, Issue 4 https://doi.org/10.1021/acscatal.5b02722	journal	March 2016
Probing Ionomer Interactions with Electrocatalyst Particles in Solution Berlinger, Sarah A.; McCloskey, Bryan D.; Weber, Adam Z. ACS Energy Letters, Vol. 6, Issue 6 https://doi.org/10.1021/acsenergylett.1c00866	journal	May 2021
Current Status and Future Development of Catalyst Materials and Catalyst Layers for Proton Exchange Membrane Fuel Cells: An Industrial Perspective Banham, Dustin; Ye, Siyu ACS Energy Letters, Vol. 2, Issue 3 https://doi.org/10.1021/acsenergylett.6b00644	journal	February 2017
Electrochemistry and the Future of the Automobile Wagner, Frederick T.; Lakshmanan, Balasubramanian; Mathias, Mark F. The Journal of Physical Chemistry Letters, Vol. 1, Issue 14 https://doi.org/10.1021/jz100553m	journal	June 2010
Investigation of a Catalyst Ink Dispersion Using Both Ultra-Small-Angle X-ray Scattering and Cryogenic TEM Xu, Fan; Zhang, HangYu; Ilavsky, Jan Langmuir, Vol. 26, Issue 24 https://doi.org/10.1021/la1028228	journal	December 2010
Effects of Block Length and Structure of Surfactant on Self-Assembly and Solution Behavior of Block Ionomer Complexes Bronich, Tatiana K.; Popov, Alexei M.; Eisenberg, Adi Langmuir, Vol. 16, Issue 2 https://doi.org/10.1021/la990628r	journal	October 1999
Electrocatalysis on Platinum Nanoparticles: Particle Size Effect on Oxygen Reduction Reaction Activity Shao, Minhua; Peles, Amra; Shoemaker, Krista Nano Letters, Vol. 11, Issue 9 https://doi.org/10.1021/nl2017459	journal	September 2011
The role of oxygen-permeable ionomer for polymer electrolyte fuel cells Jinnouchi, Ryosuke; Kudo, Kenji; Kodama, Kensaku Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-25301-3	journal	August 2021
New roads and challenges for fuel cells in heavy-duty transportation Cullen, David A.; Neyerlin, K. C.; Ahluwalia, Rajesh K. Nature Energy, Vol. 6, Issue 5 https://doi.org/10.1038/s41560-021-00775-z	journal	March 2021
Bridging the gap between highly active oxygen reduction reaction catalysts and effective catalyst layers for proton exchange membrane fuel cells Fan, Jiantao; Chen, Ming; Zhao, Zhiliang Nature Energy, Vol. 6, Issue 5 https://doi.org/10.1038/s41560-021-00824-7	journal	May 2021
Ionomer distribution control in porous carbon-supported catalyst layers for high-power and low Pt-loaded proton exchange membrane fuel cells Ott, Sebastian; Orfanidi, Alin; Schmies, Henrike Nature Materials, Vol. 19, Issue 1 https://doi.org/10.1038/s41563-019-0487-0	journal	September 2019
Achievements, challenges and perspectives on cathode catalysts in proton exchange membrane fuel cells for transportation Wang, Xiao Xia; Swihart, Mark T.; Wu, Gang Nature Catalysis, Vol. 2, Issue 7 https://doi.org/10.1038/s41929-019-0304-9	journal	July 2019
Capabilities and limitations of rotating disk electrodes versus membrane electrode assemblies in the investigation of electrocatalysts Lazaridis, Timon; Stühmeier, Björn M.; Gasteiger, Hubert A. Nature Catalysis, Vol. 5, Issue 5 https://doi.org/10.1038/s41929-022-00776-5	journal	May 2022
Record activity and stability of dealloyed bimetallic catalysts for proton exchange membrane fuel cells Han, Binghong; Carlton, Christopher E.; Kongkanand, Anusorn Energy & Environmental Science, Vol. 8, Issue 1 https://doi.org/10.1039/C4EE02144D	journal	January 2015
Atomically dispersed single iron sites for promoting Pt and Pt ₃ Co fuel cell catalysts: performance and durability improvements Qiao, Zhi; Wang, Chenyu; Li, Chenzhao Energy & Environmental Science, Vol. 14, Issue 9 https://doi.org/10.1039/D1EE01675J	journal	January 2021
Just a Dream—or Future Reality? Gasteiger, Hubert A.; Marković, Nenad M Science, Vol. 324, Issue 5923, p. 48-49 https://doi.org/10.1126/science.1172083	journal	April 2009
Quantitative Mapping of Ionomer in Catalyst Layers by Electron and X-ray Spectromicroscopy G. A. Melo, Lis; Hitchcock, Adam P.; Jankovic, Jasna ECS Transactions, Vol. 80, Issue 8 https://doi.org/10.1149/08008.0275ecst	journal	August 2017
High Performance Catalyzed Membranes of Ultra-low Pt Loadings for Polymer Electrolyte Fuel Cells Wilson, Mahlon S. Journal of The Electrochemical Society, Vol. 139, Issue 2 https://doi.org/10.1149/1.2069277	journal	January 1992
Determination of Catalyst Unique Parameters for the Oxygen Reduction Reaction in a PEMFC Neyerlin, K. C.; Gu, Wenbin; Jorne, Jacob Journal of The Electrochemical Society, Vol. 153, Issue 10 https://doi.org/10.1149/1.2266294	journal	January 2006
Measurement of Oxygen Transport Resistance in PEM Fuel Cells by Limiting Current Methods Baker, Daniel R.; Caulk, David A.; Neyerlin, Kenneth C. Journal of The Electrochemical Society, Vol. 156, Issue 9 https://doi.org/10.1149/1.3152226	journal	January 2009
Analysis of Oxygen Dissolution Rate from Gas Phase into Nafion Surface and Development of an Agglomerate Model Kudo, Kenji; Suzuki, Takahisa; Morimoto, Yu 218th ECS Meeting, ECS Transactions https://doi.org/10.1149/1.3484642	conference	January 2010
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
Surface Proton Conduction over Catalyst Support via Chemically Grafted Groups Li, Chenzhao; Liu, Yadong Journal of The Electrochemical Society, Vol. 167, Issue 16 https://doi.org/10.1149/1945-7111/abc7e6	journal	December 2020
Enhanced MEA Performance for PEMFCs under Low Relative Humidity and Low Oxygen Content Conditions via Catalyst Functionalization Xin, Le; Yang, Fan; Xie, Jian Journal of The Electrochemical Society, Vol. 164, Issue 6 https://doi.org/10.1149/2.0051707jes	journal	January 2017
Influence of Ionomer Content on Both Cell Performance and Load Cycle Durability for Polymer Electrolyte Fuel Cells Using Pt/Nb-SnO ₂ Cathode Catalyst Layers Kakinuma, Katsuyoshi; Kobayashi, Ryo; Iiyama, Akihiro Journal of The Electrochemical Society, Vol. 165, Issue 15 https://doi.org/10.1149/2.0141815jes	journal	January 2018
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
A Critical Review of Modeling Transport Phenomena in Polymer-Electrolyte Fuel Cells Weber, Adam Z.; Borup, Rodney L.; Darling, Robert M. Journal of The Electrochemical Society, Vol. 161, Issue 12 https://doi.org/10.1149/2.0751412jes	journal	January 2014
Systematic Study on the Impact of Pt Particle Size and Operating Conditions on PEMFC Cathode Catalyst Durability Yang, Z.; Ball, S.; Condit, D. Journal of The Electrochemical Society, Vol. 158, Issue 11 https://doi.org/10.1149/2.081111jes	journal	January 2011
Imaging and Microanalysis of Thin Ionomer Layers by Scanning Transmission Electron Microscopy Cullen, D. A.; Koestner, R.; Kukreja, R. S. Journal of The Electrochemical Society, Vol. 161, Issue 10 https://doi.org/10.1149/2.1091410jes	journal	January 2014
The Key to High Performance Low Pt Loaded Electrodes Orfanidi, A.; Madkikar, P.; El-Sayed, H. A. Journal of The Electrochemical Society, Vol. 164, Issue 4 https://doi.org/10.1149/2.1621704jes	journal	January 2017
Effect of Particle Size and Operating Conditions on Pt3Co PEMFC Cathode Catalyst Durability Gummalla, Mallika; Ball, Sarah; Condit, David Catalysts, Vol. 5, Issue 2 https://doi.org/10.3390/catal5020926	journal	May 2015

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