Proton Conducting Sulfonated Poly(Ionic Liquid) Block Copolymers

Sun, Rui; Agrawal, Mahesh; Neyerlin, Kenneth C.; Snyder, Joshua D.; Elabd, Yossef A.

doi:10.1021/acs.macromol.2c00468

Proton Conducting Sulfonated Poly(Ionic Liquid) Block Copolymers

Journal Article · Tue Jul 19 04:00:00 EDT 2022 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.2c00468· OSTI ID:1888784

Sun, Rui; Agrawal, Mahesh; Neyerlin, Kenneth C.; Snyder, Joshua D.; Elabd, Yossef A.

Herein, we report the synthesis of proton-conducting sulfonated poly(ionic liquid) block copolymers (S-PILBCPs) containing one block with sulfonic acid (sulfonated styrene, SS) and the other with an IL moiety (vinylbenzylmethylimidazolium bis(trifluoromethylsulfonyl)imide, VBMIm-TFSI) using reversible addition-fragmentation chain-transfer (RAFT) polymerization and post-polymerization modifications (i.e., functionalization, anion exchange reactions, and sulfonation). The S-PILBCPs uniquely conjoin the SS block with mobile protons (H+) and the PIL block with mobile anions (TFSI-), where multiple highly desired properties, including high proton conductivity (from the SS block), and high IL-philicity and oxygen solubility (from the PIL block) can exist compartmentally within a microphase separated morphology (evidenced by differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS)). High ion conductivity of 79.7 mS/cm at a PIL block composition of 21.6 mol % was observed at 80 degrees C and 90% relative humidity (RH) (comparable to the benchmark Nafion ionomer). This work successfully demonstrates the design of S-PILBCPs as a new material platform and showcases its promise as an ionomer for proton exchange membrane fuel cells (PEMFCs) as they simultaneously and compartmentally combine proton conductivity and oxygen solubility. These benefits have recently been leveraged to achieve substantial improvement in oxygen reduction reaction (ORR) activity and subsequently fuel cell performance.

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Hydrogen and Fuel Cell Technologies Office (EE-3F), Million Mile Fuel Cell Truck Consortium

DOE Contract Number:: AC36-08GO28308

OSTI ID:: 1888784

Report Number(s):: NREL/JA-5900-84064; MainId:84837; UUID:7e143845-4e3e-4b5d-b895-e9ef1ee1b06c; MainAdminID:67535

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 15 Vol. 55

Country of Publication:: United States

Language:: English

References (66)

Measuring moisture sorption and diffusion kinetics on proton exchange membranes using a gravimetric vapor sorption apparatus Burnett, Daniel J.; Garcia, Armando R.; Thielmann, Frank Journal of Power Sources, Vol. 160, Issue 1 https://doi.org/10.1016/j.jpowsour.2005.12.096	journal	September 2006
Potential-Dependent Adsorption/Desorption Behavior of Perfluorosulfonated Ionomer on a Gold Electrode Surface Studied by Cyclic Voltammetry, Electrochemical Quartz Microbalance, and Electrochemical Atomic Force Microscopy Masuda, Takuya; Ikeda, Kota; Uosaki, Kohei Langmuir, Vol. 29, Issue 7 https://doi.org/10.1021/la304705k	journal	February 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
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
Polymer Electrolytes with High Ionic Concentration for Fuel Cells and Electrolyzers Kim, Yu Seung ACS Applied Polymer Materials, Vol. 3, Issue 3 https://doi.org/10.1021/acsapm.0c01405	journal	February 2021
Lithium-Ion Transport in Poly(ionic liquid) Diblock Copolymer Electrolytes: Impact of Salt Concentration and Cation and Anion Chemistry Chen, Tzu-Ling; Lathrop, Patrick M.; Sun, Rui Macromolecules, Vol. 54, Issue 18 https://doi.org/10.1021/acs.macromol.1c00694	journal	August 2021
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
Alternative Polymer Systems for Proton Exchange Membranes (PEMs) Hickner, Michael A.; Ghassemi, Hossein; Kim, Yu Seung Chemical Reviews, Vol. 104, Issue 10 https://doi.org/10.1021/cr020711a	journal	October 2004
Liquid Water Transport in Polylactide Homo and Graft Copolymers Davis, Eric M.; Theryo, Grayce; Hillmyer, Marc A. ACS Applied Materials & Interfaces, Vol. 3, Issue 10 https://doi.org/10.1021/am2008618	journal	September 2011
Synthesis and Morphology Study of SEBS Triblock Copolymers Functionalized with Sulfonate and Phosphonate Groups for Proton Exchange Membrane Fuel Cells Date, Bhagyashree; Han, Junyoung; Park, Sungmin Macromolecules, Vol. 51, Issue 3 https://doi.org/10.1021/acs.macromol.7b01848	journal	January 2018
Water-sorption and transport properties of Nafion 117 H Morris, David R.; Sun, Xiaodong Journal of Applied Polymer Science, Vol. 50, Issue 8 https://doi.org/10.1002/app.1993.070500816	journal	November 1993
A review of polymer electrolyte membrane fuel cells: Technology, applications, and needs on fundamental research Wang, Yun; Chen, Ken S.; Mishler, Jeffrey Applied Energy, Vol. 88, Issue 4 https://doi.org/10.1016/j.apenergy.2010.09.030	journal	April 2011
Frontiers in poly(ionic liquid)s: syntheses and applications Qian, Wenjing; Texter, John; Yan, Feng Chemical Society Reviews, Vol. 46, Issue 4 https://doi.org/10.1039/C6CS00620E	journal	January 2017
Self-assembly of highly asymmetric, poly(ionic liquid)-rich diblock copolymers and the effects of simple structural modification on phase behaviour May, Alyssa W.; Shi, Zhangxing; Wijayasekara, Dilanji B. Polymer Chemistry, Vol. 10, Issue 6 https://doi.org/10.1039/C8PY01414K	journal	January 2019
Materials, technological status, and fundamentals of PEM fuel cells – A review Wang, Yun; Ruiz Diaz, Daniela Fernanda; Chen, Ken S. Materials Today, Vol. 32 https://doi.org/10.1016/j.mattod.2019.06.005	journal	January 2020
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
Block Copolymers for Fuel Cells Elabd, Yossef A.; Hickner, Michael A. Macromolecules, Vol. 44, Issue 1 https://doi.org/10.1021/ma101247c	journal	January 2011
Developments of highly proton-conductive sulfonated polymers for proton exchange membrane fuel cells Liu, Ying-Ling Polymer Chemistry, Vol. 3, Issue 6 https://doi.org/10.1039/c2py20106b	journal	January 2012
Investigation of Water Diffusion Mechanisms in Relation to Polymer Relaxations in Polyamides Preda, Florentina-Maria; Alegría, Angel; Bocahut, Anthony Macromolecules, Vol. 48, Issue 16 https://doi.org/10.1021/acs.macromol.5b01295	journal	August 2015
Spectroscopic and Theoretical Study of (CF ₃ SO ₂ ) ₂ N ^- (TFSI ^- ) and (CF ₃ SO ₂ ) ₂ NH (HTFSI) Rey, I.; Johansson, P.; Lindgren, J. The Journal of Physical Chemistry A, Vol. 102, Issue 19 https://doi.org/10.1021/jp980375v	journal	May 1998
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
Boosting Performance of Low Temperature Fuel Cell Catalysts by Subtle Ionic Liquid Modification Zhang, Gui-Rong; Munoz, Macarena; Etzold, Bastian J. M. ACS Applied Materials & Interfaces, Vol. 7, Issue 6 https://doi.org/10.1021/am5074003	journal	February 2015
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
Permeation, sorption, and diffusion of water in ethyl cellulose Wellons, J. D.; Stannett, V. Journal of Polymer Science Part A-1: Polymer Chemistry, Vol. 4, Issue 3 https://doi.org/10.1002/pol.1966.150040313	journal	March 1966
Ion Percolation and Insulator-to-Conductor Transition in Nafion Perfluorosulfonic Acid Membranes Hsu, William Y.; Barkley, John R.; Meakin, Paul Macromolecules, Vol. 13, Issue 1 https://doi.org/10.1021/ma60073a041	journal	January 1980
Poly(ionic liquid)s: An update Yuan, Jiayin; Mecerreyes, David; Antonietti, Markus Progress in Polymer Science, Vol. 38, Issue 7 https://doi.org/10.1016/j.progpolymsci.2013.04.002	journal	July 2013
Polymerized ionic liquid block copolymers for electrochemical energy Meek, Kelly M.; Elabd, Yossef A. Journal of Materials Chemistry A, Vol. 3, Issue 48 https://doi.org/10.1039/C5TA07170D	journal	January 2015
Sulfonated pentablock terpolymers as membranes and ionomers in hydrogen fuel cells Hwang, Monica; Nixon, Kevin; Sun, Rui Journal of Membrane Science, Vol. 633 https://doi.org/10.1016/j.memsci.2021.119330	journal	September 2021
Solid‐State Alkaline Fuel Cell Performance of Pentablock Terpolymer with Methylpyrrolidinium Cations as Anion Exchange Membrane and Ionomer Hwang, M.; Sun, R.; Willis, C. Fuel Cells, Vol. 20, Issue 5 https://doi.org/10.1002/fuce.202000092	journal	October 2020
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
Impact of ionic liquid on lithium ion battery with a solid poly(ionic liquid) pentablock terpolymer as electrolyte and separator Chen, Tzu-Ling; Sun, Rui; Willis, Carl Polymer, Vol. 209 https://doi.org/10.1016/j.polymer.2020.122975	journal	November 2020
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
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
The Triple Phase Boundary O’Hayre, Ryan; Barnett, David M.; Prinz, Fritz B. Journal of The Electrochemical Society, Vol. 152, Issue 2 https://doi.org/10.1149/1.1851054	journal	January 2005
Non-Fickian Diffusion of Water in Nafion Hallinan, Daniel T.; De Angelis, Maria Grazia; Giacinti Baschetti, Marco Macromolecules, Vol. 43, Issue 10 https://doi.org/10.1021/ma100047z	journal	May 2010
Irena : tool suite for modeling and analysis of small-angle scattering Ilavsky, Jan; Jemian, Peter R. Journal of Applied Crystallography, Vol. 42, Issue 2 https://doi.org/10.1107/S0021889809002222	journal	February 2009
A comprehensive review of Pt electrocatalysts for the oxygen reduction reaction: Nanostructure, activity, mechanism and carbon support in PEM fuel cells Sui, Sheng; Wang, Xiaoying; Zhou, Xintong Journal of Materials Chemistry A, Vol. 5, Issue 5 https://doi.org/10.1039/C6TA08580F	journal	January 2017
Thermogravimetric characterization of highly sulfonated poly(styrene–isobutylene–styrene) block copolymers: Effects of sulfonation and counter-ion substitution Suleiman, David; Napadensky, Eugene; Sloan, James M. Thermochimica Acta, Vol. 460, Issue 1-2 https://doi.org/10.1016/j.tca.2007.05.012	journal	August 2007
Characterization of a Sulfonated Poly(Ionic Liquid) Block Copolymer as an Ionomer for Proton Exchange Membrane Fuel Cells using Rotating Disk Electrode Gawas, Ramchandra; Sun, Rui; Li, Yawei Journal of The Electrochemical Society, Vol. 168, Issue 12 https://doi.org/10.1149/1945-7111/ac4375	journal	December 2021
Oxygen Reduction Reaction at Three-Phase Interfaces Subbaraman, Ram; Strmcnik, Dusan; Paulikas, Arvydas P. ChemPhysChem, Vol. 11, Issue 13 https://doi.org/10.1002/cphc.201000190	journal	July 2010
Tailoring electrode microstructure via ink content to enable improved rated power performance for platinum cobalt/high surface area carbon based polymer electrolyte fuel cells Van Cleve, Tim; Wang, Guanxiong; Mooney, Mason Journal of Power Sources, Vol. 482 https://doi.org/10.1016/j.jpowsour.2020.228889	journal	January 2021
Unexplained transport resistances for low-loaded fuel-cell catalyst layers Weber, Adam Z.; Kusoglu, Ahmet J. Mater. Chem. A, Vol. 2, Issue 41 https://doi.org/10.1039/C4TA02952F	journal	January 2014
Nika : software for two-dimensional data reduction Ilavsky, Jan Journal of Applied Crystallography, Vol. 45, Issue 2 https://doi.org/10.1107/S0021889812004037	journal	March 2012
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
Experimental Vibrational Study of Imidazolium-Based Ionic Liquids: Raman and Infrared Spectra of 1-Ethyl-3-methylimidazolium Bis(Trifluoromethylsulfonyl)imide and 1-Ethyl-3-methylimidazolium Ethylsulfate Kiefer, Johannes; Fries, Juergen; Leipertz, Alfred Applied Spectroscopy, Vol. 61, Issue 12 https://doi.org/10.1366/000370207783292000	journal	December 2007
Lithium ion conducting polymerized ionic liquid pentablock terpolymers as solid-state electrolytes Chen, Tzu-Ling; Sun, Rui; Willis, Carl Polymer, Vol. 161 https://doi.org/10.1016/j.polymer.2018.12.013	journal	January 2019
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
Ionic liquids in electrocatalysis Zhang, Gui-Rong; Etzold, Bastian J. M. Journal of Energy Chemistry, Vol. 25, Issue 2 https://doi.org/10.1016/j.jechem.2016.01.007	journal	March 2016
Clustering of solvents in membranes and its influence on membrane transport properties Nguyen, Q. T.; Favre, E.; Ping, Z. H. Journal of Membrane Science, Vol. 113, Issue 1 https://doi.org/10.1016/0376-7388(95)00219-7	journal	May 1996
Water Clustering in Glassy Polymers Davis, Eric M.; Elabd, Yossef A. The Journal of Physical Chemistry B, Vol. 117, Issue 36 https://doi.org/10.1021/jp405388d	journal	August 2013
Block copolymer ionomers: 1. Synthesis and physical properties of sulphonated poly(styrene-ethylene/butylene-styrene) Weiss, R. A.; Sen, Ashish; Willis, C. L. Polymer, Vol. 32, Issue 10 https://doi.org/10.1016/0032-3861(91)90378-V	journal	January 1991
Recent Progresses in Oxygen Reduction Reaction Electrocatalysts for Electrochemical Energy Applications Li, Yahao; Li, Qingyu; Wang, Hongqiang Electrochemical Energy Reviews, Vol. 2, Issue 4 https://doi.org/10.1007/s41918-019-00052-4	journal	October 2019
Water sorption and transport in blends of polyethyloxazoline and polyethersulfone Schult, K. A.; Paul, D. R. Journal of Polymer Science Part B: Polymer Physics, Vol. 35, Issue 6 https://doi.org/10.1002/(SICI)1099-0488(19970430)35:6<993::AID-POLB13>3.0.CO;2-A	journal	April 1997
Ionic Liquid Additives for the Mitigation of Nafion Specific Adsorption on Platinum Li, Yawei; Intikhab, Saad; Malkani, Arnav ACS Catalysis, Vol. 10, Issue 14 https://doi.org/10.1021/acscatal.0c01243	journal	June 2020
Synthesis and High Alkaline Chemical Stability of Polyionic Liquids with Methylpyrrolidinium, Methylpiperidinium, Methylazepanium, Methylazocanium, and Methylazonanium Cations Sun, Rui; Elabd, Yossef A. ACS Macro Letters https://doi.org/10.1021/acsmacrolett.9b00039	journal	April 2019
Impact of ionomer resistance in nanofiber-nanoparticle electrodes for ultra-low platinum fuel cells Hwang, Monica; Elabd, Yossef A. International Journal of Hydrogen Energy, Vol. 44, Issue 12 https://doi.org/10.1016/j.ijhydene.2019.01.083	journal	March 2019
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
Poly(ionic liquid)s: Polymers expanding classical property profiles Yuan, Jiayin; Antonietti, Markus Polymer, Vol. 52, Issue 7 https://doi.org/10.1016/j.polymer.2011.01.043	journal	March 2011
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
Hydroxide conducting polymerized ionic liquid pentablock terpolymer anion exchange membranes with methylpyrrolidinium cations Meek, Kelly M.; Sun, Rui; Willis, Carl Polymer, Vol. 134 https://doi.org/10.1016/j.polymer.2017.11.050	journal	January 2018
Recent Advances in Electrocatalysts for Oxygen Reduction Reaction Shao, Minhua; Chang, Qiaowan; Dodelet, Jean-Pol Chemical Reviews, Vol. 116, Issue 6 https://doi.org/10.1021/acs.chemrev.5b00462	journal	February 2016
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 ACS Energy Letters, Vol. 5, Issue 6 https://doi.org/10.1021/acsenergylett.0c00532	journal	April 2020
100th Anniversary of Macromolecular Science Viewpoint: Block Copolymers with Tethered Acid Groups: Challenges and Opportunities Kang, Sejong; Park, Moon Jeong ACS Macro Letters, Vol. 9, Issue 11 https://doi.org/10.1021/acsmacrolett.0c00629	journal	October 2020
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
Sulfonation and characterization of poly(styrene-isobutylene-styrene) triblock copolymers at high ion-exchange capacities Elabd, Yossef A.; Napadensky, Eugene Polymer, Vol. 45, Issue 9 https://doi.org/10.1016/j.polymer.2004.02.061	journal	April 2004
Improving the Overall Characteristics of Proton Exchange MembranesviaNanophase Separation Technologies: A Progress Review Hu, Y.; Li, X.; Yan, L. Fuel Cells, Vol. 17, Issue 1 https://doi.org/10.1002/fuce.201600172	journal	February 2017

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DIRECT ENERGY CONVERSION
anion exchange reactions
functionalization
reversible addition-fragmentation chain-transfer polymerization
sulfonated poly(ionic liquid) block copolymers
sulfonation
sulfonic acid

Proton Conducting Sulfonated Poly(Ionic Liquid) Block Copolymers

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