Modifying the Electrocatalyst–Ionomer Interface via Sulfonated Poly(ionic liquid) Block Copolymers to Enable High-Performance Polymer Electrolyte Fuel Cells

Li, Yawei; Van Cleve, Tim; Sun, Rui; Gawas, Ramchandra; Wang, Guanxiong; Tang, Maureen; Elabd, Yossef A.; Snyder, Joshua; Neyerlin, K. C.

doi:10.1021/acsenergylett.0c00532

Title: Modifying the Electrocatalyst–Ionomer Interface via Sulfonated Poly(ionic liquid) Block Copolymers to Enable High-Performance Polymer Electrolyte Fuel Cells

Journal Article · Wed Apr 29 00:00:00 EDT 2020 · ACS Energy Letters

DOI:https://doi.org/10.1021/acsenergylett.0c00532· OSTI ID:2317691

Li, Yawei ^[1];

^[1]; Sun, Rui ^[2]; Gawas, Ramchandra ^[3]; Wang, Guanxiong ^[1];

^[3];

^[2];

^[3];

^[1]

Chemistry and Nanoscience Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States
Department of Chemical Engineering, Texas A&M University, College Station, Texas 77843, United States
Department of Chemical and Biological Engineering, Drexel University, Philadelphia, Pennsylvania 19104, United States

In this work, polymer electrolyte membrane fuel cell (PEMFC) electrodes with a 0.07 mg_Pt cm^–2 Pt/Vulcan electrocatalyst loading, containing only a sulfonated poly(ionic liquid) block copolymer (SPILBCP) ionomer, were fabricated and achieved a ca. 2× enhancement of kinetic performance through the suppression of Pt surface oxidation. However, SPILBCP electrodes lost over 70% of their electrochemical active area at 30% RH because of poor ionomer network connectivity. To combat these effects, electrodes made with a mix of Nafion/SPILBCP ionomers were developed. Mixed Nafion/SPILBCP electrodes resulted in a substantial improvement in MEA performance across the kinetic and mass transport-limited regions. Notably, this is the first time that specific activity values determined from an MEA were observed to be on par with prior half-cell results for Nafion-free Pt/Vulcan systems. These findings present a prospective strategy to improve the overall performance of MEAs fabricated with surface accessible electrocatalysts, providing a pathway to tailor the local electrocatalyst/ionomer interface.

View Journal Article

Cite

Export

Save

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States); Drexel Univ., Philadelphia, PA (United States)

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

Grant/Contract Number:: AC36-08GO28308; EE0008434

OSTI ID:: 2317691

Alternate ID(s):: OSTI ID: 1659821; OSTI ID: 2228289

Report Number(s):: NREL/JA-5900-76372

Journal Information:: ACS Energy Letters, Journal Name: ACS Energy Letters Vol. 5 Journal Issue: 6; ISSN 2380-8195

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 38 works

Citation information provided by
Web of Science

References (51)

Effect of Ionic Liquid Modification on the ORR Performance and Degradation Mechanism of Trimetallic PtNiMo/C Catalysts George, Michael; Zhang, Gui-Rong; Schmitt, Nicolai ACS Catalysis, Vol. 9, Issue 9 https://doi.org/10.1021/acscatal.9b01772	journal	August 2019
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
Changing the Activity of Electrocatalysts for Oxygen Reduction by Tuning the Surface Electronic Structure Stamenkovic, Vojislav; Mun, Bongjin Simon; Mayrhofer, Karl J. J. Angewandte Chemie International Edition, Vol. 45, Issue 18 https://doi.org/10.1002/anie.200504386	journal	April 2006
Three Phase Interfaces at Electrified Metal−Solid Electrolyte Systems 1. Study of the Pt( hkl )−Nafion Interface Subbaraman, Ram; Strmcnik, Dusan; Stamenkovic, Vojislav The Journal of Physical Chemistry C, Vol. 114, Issue 18 https://doi.org/10.1021/jp100814x	journal	April 2010
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
Effect of the Side-Chain Structure of Perfluoro-Sulfonic Acid Ionomers on the Oxygen Reduction Reaction on the Surface of Pt Kodama, Kensaku; Motobayashi, Kenta; Shinohara, Akihiro ACS Catalysis, Vol. 8, Issue 1 https://doi.org/10.1021/acscatal.7b03571	journal	December 2017
Polymerized ionic liquid diblock copolymer as an ionomer and anion exchange membrane for alkaline fuel cells Nykaza, Jacob R.; Benjamin, Rishon; Meek, Kelly M. Chemical Engineering Science, Vol. 154 https://doi.org/10.1016/j.ces.2016.05.041	journal	November 2016
Impact of Catalyst Ink Dispersing Methodology on Fuel Cell Performance Using in-Situ X-ray Scattering Wang, Min; Park, Jae Hyung; Kabir, Sadia ACS Applied Energy Materials, Vol. 2, Issue 9 https://doi.org/10.1021/acsaem.9b01037	journal	July 2019
Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces Chen, C.; Kang, Y.; Huo, Z. Science, Vol. 343, Issue 6177 https://doi.org/10.1126/science.1249061	journal	February 2014
Electrode for proton exchange membrane fuel cells: A review Majlan, E. H.; Rohendi, D.; Daud, W. R. W. Renewable and Sustainable Energy Reviews, Vol. 89 https://doi.org/10.1016/j.rser.2018.03.007	journal	June 2018
Oxygen Reduction Reaction Measurements on Platinum Electrocatalysts Utilizing Rotating Disk Electrode Technique: II. Influence of Ink Formulation, Catalyst Layer Uniformity and Thickness Shinozaki, Kazuma; Zack, Jason W.; Pylypenko, Svitlana Journal of The Electrochemical Society, Vol. 162, Issue 12 https://doi.org/10.1149/2.0551512jes	journal	January 2015
Sulfonated Polymerized Ionic Liquid Block Copolymers Meek, Kelly M.; Elabd, Yossef A. Macromolecular Rapid Communications, Vol. 37, Issue 14 https://doi.org/10.1002/marc.201600089	journal	April 2016
Oxygen Reduction Kinetics in Low and Medium Temperature Acid Environment: Correlation of Water Activation and Surface Properties in Supported Pt and Pt Alloy Electrocatalysts Murthi, Vivek S.; Urian, R. Craig; Mukerjee, Sanjeev The Journal of Physical Chemistry B, Vol. 108, Issue 30 https://doi.org/10.1021/jp048985k	journal	July 2004
Improved electrochemical performance of Fe-N-C catalysts through ionic liquid modification in alkaline media Martinaiou, Ioanna; Wolker, Thomas; Shahraei, Ali Journal of Power Sources, Vol. 375 https://doi.org/10.1016/j.jpowsour.2017.07.028	journal	January 2018
Oxygen Reduction at a Cu-Modified Pt(111) Model Electrocatalyst in Contact with Nafion Polymer Tymoczko, Jakub; Calle-Vallejo, Federico; Colic, Viktor ACS Catalysis, Vol. 4, Issue 10 https://doi.org/10.1021/cs501037y	journal	September 2014
Electrocatalyst approaches and challenges for automotive fuel cells Debe, Mark K. Nature, Vol. 486, Issue 7401 https://doi.org/10.1038/nature11115	journal	June 2012
Suppression of oxygen reduction reaction activity on Pt-based electrocatalysts from ionomer incorporation Shinozaki, Kazuma; Morimoto, Yu; Pivovar, Bryan S. Journal of Power Sources, Vol. 325 https://doi.org/10.1016/j.jpowsour.2016.06.062	journal	September 2016
Oxygen reduction in nanoporous metal–ionic liquid composite electrocatalysts Snyder, J.; Fujita, T.; Chen, M. W. Nature Materials, Vol. 9, Issue 11 https://doi.org/10.1038/nmat2878	journal	October 2010
Kinetics of Oxygen Reduction on Pt(hkl) Electrodes: Implications for the Crystallite Size Effect with Supported Pt Electrocatalysts Markovic, Nenad Journal of The Electrochemical Society, Vol. 144, Issue 5 https://doi.org/10.1149/1.1837646	journal	January 1997
Morphological Instability in Topologically Complex, Three-Dimensional Electrocatalytic Nanostructures Li, Yawei; Hart, James L.; Taheri, Mitra L. ACS Catalysis, Vol. 7, Issue 11 https://doi.org/10.1021/acscatal.7b02398	journal	October 2017
Dictating Pt-Based Electrocatalyst Performance in Polymer Electrolyte Fuel Cells, from Formulation to Application Van Cleve, Tim; Khandavalli, Sunilkumar; Chowdhury, Anamika ACS Applied Materials & Interfaces, Vol. 11, Issue 50 https://doi.org/10.1021/acsami.9b17614	journal	November 2019
Pt-Oxide Coverage-Dependent Oxygen Reduction Reaction (ORR) Kinetics Subramanian, N. P.; Greszler, T. A.; Zhang, J. Journal of The Electrochemical Society, Vol. 159, Issue 5 https://doi.org/10.1149/2.088205jes	journal	January 2012
Enhancing Pt/C Catalysts for the Oxygen Reduction Reaction with Protic Ionic Liquids: The Effect of Anion Structure Huang, Kan; Song, Tangqiumei; Morales-Collazo, Oscar Journal of The Electrochemical Society, Vol. 164, Issue 13 https://doi.org/10.1149/2.1071713jes	journal	January 2017
Ordered Pt ₃ Co Intermetallic Nanoparticles Derived from Metal–Organic Frameworks for Oxygen Reduction Wang, Xiao Xia; Hwang, Sooyeon; Pan, Yung-Tin Nano Letters, Vol. 18, Issue 7 https://doi.org/10.1021/acs.nanolett.8b00978	journal	June 2018
Tuning the Electrocatalytic Performance of Ionic Liquid Modified Pt Catalysts for the Oxygen Reduction Reaction via Cationic Chain Engineering Zhang, Gui-Rong; Wolker, Thomas; Sandbeck, Daniel J. S. ACS Catalysis, Vol. 8, Issue 9 https://doi.org/10.1021/acscatal.8b02018	journal	July 2018
Proton Conduction and Oxygen Reduction Kinetics in PEM Fuel Cell Cathodes: Effects of Ionomer-to-Carbon Ratio and Relative Humidity Liu, Yuxiu; Murphy, Michael W.; Baker, Daniel R. Journal of The Electrochemical Society, Vol. 156, Issue 8 https://doi.org/10.1149/1.3143965	journal	January 2009
Accelerating Oxygen-Reduction Catalysts through Preventing Poisoning with Non-Reactive Species by Using Hydrophobic Ionic Liquids Zhang, Gui-Rong; Munoz, Macarena; Etzold, Bastian J. M. Angewandte Chemie International Edition, Vol. 55, Issue 6 https://doi.org/10.1002/anie.201508338	journal	December 2015
Improved Oxygen Reduction Activity on Pt₃Ni(111) via Increased Surface Site Availability Stamenkovic, V. R.; Fowler, B.; Mun, B. S. Science, Vol. 315, Issue 5811, p. 493-497 https://doi.org/10.1126/science.1135941	journal	January 2007
Evolution of Ionomer Morphology from Dispersion to Film: An in Situ X-ray Study Dudenas, Peter J.; Kusoglu, Ahmet Macromolecules, Vol. 52, Issue 20 https://doi.org/10.1021/acs.macromol.9b01024	journal	October 2019
Fuel Cell Catalyst Layers: A Polymer Science Perspective Holdcroft, Steven Chemistry of Materials, Vol. 26, Issue 1 https://doi.org/10.1021/cm401445h	journal	July 2013
Oxygenophilic ionic liquids promote the oxygen reduction reaction in Pt-free carbon electrocatalysts Qiao, Mo; Tang, Cheng; Tanase, Liviu Cristian Materials Horizons, Vol. 4, Issue 5 https://doi.org/10.1039/C7MH00298J	journal	January 2017
Effect of alkaline exchange polymerized ionic liquid block copolymer ionomers on the kinetics of fuel cell half reactions Nykaza, Jacob R.; Li, Yawei; Elabd, Yossef A. Journal of Electroanalytical Chemistry, Vol. 783 https://doi.org/10.1016/j.jelechem.2016.11.024	journal	December 2016
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
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
Elementary Mechanisms in Electrocatalysis: Revisiting the ORR Tafel Slope Holewinski, Adam; Linic, Suljo Journal of The Electrochemical Society, Vol. 159, Issue 11 https://doi.org/10.1149/2.022211jes	journal	January 2012
Characterization of Nanoporous Metal-Ionic Liquid Composites for the Electrochemical Oxygen Reduction Reaction Benn, E.; Uvegi, H.; Erlebacher, J. Journal of The Electrochemical Society, Vol. 162, Issue 10 https://doi.org/10.1149/2.0161510jes	journal	January 2015
Rheological Investigation on the Microstructure of Fuel Cell Catalyst Inks Khandavalli, Sunilkumar; Park, Jae Hyung; Kariuki, Nancy N. ACS Applied Materials & Interfaces, Vol. 10, Issue 50 https://doi.org/10.1021/acsami.8b15039	journal	December 2018
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
Oxygen Reduction Reaction Performance of [MTBD][beti]-Encapsulated Nanoporous NiPt Alloy Nanoparticles Snyder, Joshua; Livi, Kenneth; Erlebacher, Jonah Advanced Functional Materials, Vol. 23, Issue 44 https://doi.org/10.1002/adfm.201301144	journal	June 2013
Surface Composition Effects in Electrocatalysis: Kinetics of Oxygen Reduction on Well-Defined Pt ₃ Ni and Pt ₃ Co Alloy Surfaces Stamenković, V.; Schmidt, T. J.; Ross, P. N. The Journal of Physical Chemistry B, Vol. 106, Issue 46 https://doi.org/10.1021/jp021182h	journal	November 2002
The Complex Inhibiting Role of Surface Oxide in the Oxygen Reduction Reaction Coleman, Eric J.; Co, Anne C. ACS Catalysis, Vol. 5, Issue 12 https://doi.org/10.1021/acscatal.5b02122	journal	November 2015
Tuning the Ionomer Distribution in the Fuel Cell Catalyst Layer with Scaling the Ionomer Aggregate Size in Dispersion Doo, Gisu; Lee, Ji Hye; Yuk, Seongmin ACS Applied Materials & Interfaces, Vol. 10, Issue 21 https://doi.org/10.1021/acsami.8b01751	journal	May 2018
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
Acetonitrile Adsorption on Pt Single-Crystal Electrodes and Its Effect on Oxygen Reduction Reaction in Acidic and Alkaline Aqueous Solutions Briega-Martos, Valentín; Costa-Figueiredo, Marta; Orts, José M. The Journal of Physical Chemistry C, Vol. 123, Issue 4 https://doi.org/10.1021/acs.jpcc.8b10690	journal	January 2019
Platinum Monolayer Fuel Cell Electrocatalysts Adzic, R. R.; Zhang, J.; Sasaki, K. Topics in Catalysis, Vol. 46, Issue 3-4, p. 249-262 https://doi.org/10.1007/s11244-007-9003-x	journal	November 2007
Nanostructure/Swelling Relationships of Bulk and Thin-Film PFSA Ionomers Kusoglu, Ahmet; Dursch, Thomas J.; Weber, Adam Z. Advanced Functional Materials, Vol. 26, Issue 27 https://doi.org/10.1002/adfm.201600861	journal	May 2016
Influence of Equivalent Weight of Ionomer on Local Oxygen Transport Resistance in Cathode Catalyst Layers Ono, Yoshitaka; Ohma, Atsushi; Shinohara, Kazuhiko Journal of The Electrochemical Society, Vol. 160, Issue 8 https://doi.org/10.1149/2.040308jes	journal	January 2013
Ionic Liquid-Modified Microporous ZnCoNC-Based Electrocatalysts for Polymer Electrolyte Fuel Cells Wang, Min; Zhang, Huixin; Thirunavukkarasu, Gnanavel ACS Energy Letters, Vol. 4, Issue 9 https://doi.org/10.1021/acsenergylett.9b01407	journal	August 2019
Effect of Acetonitrile Contamination on Long-Term Degradation of Proton Exchange Membrane Fuel Cells Zhai, Yunfeng; Ge, Junjie; Qi, Jing Journal of The Electrochemical Society, Vol. 165, Issue 6 https://doi.org/10.1149/2.0221806jes	journal	January 2018
Sequential Capacitive Deposition of Ionic Liquids for Conformal Thin Film Coatings on Oxygen Reduction Reaction Electrocatalysts Li, Yawei; Hart, James; Profitt, Lauren ACS Catalysis, Vol. 9, Issue 10 https://doi.org/10.1021/acscatal.9b03157	journal	September 2019
Boosting the Oxygen Reduction Electrocatalytic Performance of Nonprecious Metal Nanocarbons via Triple Boundary Engineering Using Protic Ionic Liquids Qiao, Mo; Ferrero, Guillermo A.; Fernández Velasco, Leticia ACS Applied Materials & Interfaces, Vol. 11, Issue 12 https://doi.org/10.1021/acsami.8b18375	journal	February 2019

Similar Records

Characterization of a Sulfonated Poly(Ionic Liquid) Block Copolymer as an Ionomer for Proton Exchange Membrane Fuel Cells using Rotating Disk Electrode

Journal Article · Fri Dec 24 00:00:00 EST 2021 · Journal of the Electrochemical Society · OSTI ID:2317691

Gawas, Ramchandra; Sun, Rui; Li, Yawei; +4 more

Characterization of a Sulfonated Poly(Ionic Liquid) Block Copolymer as an Ionomer for Proton Exchange Membrane Fuel Cells using Rotating Disk Electrode

Journal Article · Fri Dec 24 00:00:00 EST 2021 · Journal of the Electrochemical Society · OSTI ID:2317691

Gawas, Ramchandra; Sun, Rui; Li, Yawei; +4 more

Proton Conducting Sulfonated Poly(Ionic Liquid) Block Copolymers

Journal Article · Tue Jul 19 00:00:00 EDT 2022 · Macromolecules · OSTI ID:2317691

Sun, Rui; Agrawal, Mahesh; Neyerlin, Kenneth C.; +2 more

Related Subjects

25 ENERGY STORAGE
electrocatalyst
PILBCP
poly(ionic liquid) block copolymer
polymer electrolyte membrane fuel cell

Title: Modifying the Electrocatalyst–Ionomer Interface via Sulfonated Poly(ionic liquid) Block Copolymers to Enable High-Performance Polymer Electrolyte Fuel Cells

Citation Formats

References (51)

Similar Records

Related Subjects