How does a small structural change of anode ionomer make a big difference in alkaline membrane fuel cell performance?

Park, Eun Joo; Lee, Albert Sung Soo; Leonard, Daniel Philip; Li, Dongguo; Jeon, Jong Yeob; Bae, Chul Sung; Kim, Yu Seung

doi:10.1039/c9ta10157h

Title: How does a small structural change of anode ionomer make a big difference in alkaline membrane fuel cell performance?

Journal Article · Mon Oct 14 00:00:00 EDT 2019 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/c9ta10157h· OSTI ID:1764206

^[1];

^[1]; Leonard, Daniel Philip ^[1];

^[1]; Jeon, Jong Yeob ^[2]; Bae, Chul Sung ^[2];

^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Rensselaer Polytechnic Inst., Troy, NY (United States)

Anode ionomers of alkaline membrane fuel cells (AMFCs) play a critical role in hydrogen and water transport thus affecting cell performance and durability. Here, we modified a quaternized poly(biphenyl alkylene) ionomer with two chemical structural variations to increase hydrogen access to the AMFC anode: first, we introduced the symmetric dimethyl groups in the polymer backbone to increase polymer fractional free volume. Second, we replaced hydroxide-conducting alkyl trimethylammonium with alkyl triethylammonium to reduce cation–hydroxide–water co-adsorption on the hydrogen oxidation catalyst to increase hydrogen access to the co-adsorbed layer. Furthermore, we compared the performance benefits of the two structural variations through operating AMFCs under H₂/O₂ conditions. The membrane electrode assembly employing the modified poly(biphenyl alkylene) ionomer at the anode exhibited >1500 mW cm^-2 peak power density at 80 °C with stable short-term durability (>100 h) under a constant current density of 0.6 A cm^-2. This study provides an essential insight into designing anode ionomer of highly performing AMFCs.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE). Fuel Cell Technologies Program; USDOE

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 1764206

Alternate ID(s):: OSTI ID: 1571303

Report Number(s):: LA-UR-20-21325

Journal Information:: Journal of Materials Chemistry. A, Vol. 7, Issue 43; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 48 works

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References (52)

A one-shot sequence for high-resolution diffusion-ordered spectroscopy Pelta, Michelle D.; Morris, Gareth A.; Stchedroff, Marc J. Magnetic Resonance in Chemistry, Vol. 40, Issue 13 https://doi.org/10.1002/mrc.1107	journal	January 2002
Preparation of radiation-grafted powders for use as anion exchange ionomers in alkaline polymer electrolyte fuel cells Poynton, Simon D.; Slade, Robert C. T.; Omasta, Travis J. J. Mater. Chem. A, Vol. 2, Issue 14 https://doi.org/10.1039/C4TA00558A	journal	January 2014
Robust Hydroxide Ion Conducting Poly(biphenyl alkylene)s for Alkaline Fuel Cell Membranes Lee, Woo-Hyung; Kim, Yu Seung; Bae, Chulsung ACS Macro Letters, Vol. 4, Issue 8 https://doi.org/10.1021/acsmacrolett.5b00375	journal	July 2015
Anion conducting multiblock copolymer membranes with partial fluorination and long head-group tethers Liu, Lisha; Ahlfield, John; Tricker, Andrew Journal of Materials Chemistry A, Vol. 4, Issue 41 https://doi.org/10.1039/C6TA06653D	journal	January 2016
Cationic Polyelectrolytes, Stable in 10 M KOH _aq at 100 °C Fan, Jiantao; Wright, Andrew G.; Britton, Benjamin ACS Macro Letters, Vol. 6, Issue 10 https://doi.org/10.1021/acsmacrolett.7b00679	journal	September 2017
Resonance Stabilized Perfluorinated Ionomers for Alkaline Membrane Fuel Cells Kim, Dae Sik; Fujimoto, Cy H.; Hibbs, Michael R. Macromolecules, Vol. 46, Issue 19, p. 7826-7833 https://doi.org/10.1021/ma401568f	journal	September 2013
Alkaline Stability of Quaternary Ammonium Cations for Alkaline Fuel Cell Membranes and Ionic Liquids Marino, M. G.; Kreuer, K. D. ChemSusChem, Vol. 8, Issue 3 https://doi.org/10.1002/cssc.201403022	journal	November 2014
NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist Fulmer, Gregory R.; Miller, Alexander J. M.; Sherden, Nathaniel H. Organometallics, Vol. 29, Issue 9 https://doi.org/10.1021/om100106e	journal	May 2010
Determination of Molecular Self-Diffusion Coefficients Using Pulsed-Field-Gradient NMR: An Experiment for Undergraduate Physical Chemistry Laboratory Harmon, Jennifer; Coffman, Cierra; Villarrial, Spring Journal of Chemical Education, Vol. 89, Issue 6 https://doi.org/10.1021/ed200471k	journal	March 2012
Quaternized aryl ether-free polyaromatics for alkaline membrane fuel cells: synthesis, properties, and performance – a topical review Park, Eun Joo; Kim, Yu Seung Journal of Materials Chemistry A, Vol. 6, Issue 32 https://doi.org/10.1039/C8TA05428B	journal	January 2018
Diffusivity enhancement of water vapor in poly(vinyl alcohol)–fumed silica nano-composite membranes: Correlation with polymer crystallinity and free-volume properties Lue, S.; Lee, D.; Chen, J. Journal of Membrane Science, Vol. 325, Issue 2 https://doi.org/10.1016/j.memsci.2008.09.015	journal	December 2008
Synthesis of Aromatic Anion Exchange Membranes by Friedel–Crafts Bromoalkylation and Cross-Linking of Polystyrene Block Copolymers Jeon, Jong Yeob; Park, Sungmin; Han, Junyoung Macromolecules, Vol. 52, Issue 5 https://doi.org/10.1021/acs.macromol.8b02355	journal	February 2019
An electron-beam-grafted ETFE alkaline anion-exchange membrane in metal-cation-free solid-state alkaline fuel cells Varcoe, J.; Slade, R. Electrochemistry Communications, Vol. 8, Issue 5 https://doi.org/10.1016/j.elecom.2006.03.027	journal	May 2006
Correlation and prediction of gas permeability in glassy polymer membrane materials via a modified free volume based group contribution method Park, J. Y.; Paul, D. R. Journal of Membrane Science, Vol. 125, Issue 1 https://doi.org/10.1016/S0376-7388(96)00061-0	journal	March 1997
Precision Synthesis of Narrow Polydispersity, Ultrahigh Molecular Weight Linear Aromatic Polymers by A ₂ + B ₂ Nonstoichiometric Step-Selective Polymerization Cruz, Alfredo R.; Hernandez, M. Carmen G.; Guzmán-Gutiérrez, Maria T. Macromolecules, Vol. 45, Issue 17 https://doi.org/10.1021/ma301691f	journal	August 2012
Poly(terphenylene) Anion Exchange Membranes: The Effect of Backbone Structure on Morphology and Membrane Property Lee, Woo-Hyung; Park, Eun Joo; Han, Junyoung ACS Macro Letters, Vol. 6, Issue 5 https://doi.org/10.1021/acsmacrolett.7b00148	journal	April 2017
Adsorption of Polyaromatic Backbone Impacts the Performance of Anion Exchange Membrane Fuel Cells Matanovic, Ivana; Maurya, Sandip; Park, Eun Joo Chemistry of Materials, Vol. 31, Issue 11 https://doi.org/10.1021/acs.chemmater.9b01092	journal	May 2019
Pulsed-field gradient nuclear magnetic resonance as a tool for studying translational diffusion: Part 1. Basic theory Price, William S. Concepts in Magnetic Resonance, Vol. 9, Issue 5 https://doi.org/10.1002/(SICI)1099-0534(1997)9:5<299::AID-CMR2>3.0.CO;2-U	journal	January 1997
Backbone stability of quaternized polyaromatics for alkaline membrane fuel cells Fujimoto, Cy; Kim, Dae-Sik; Hibbs, Michael Journal of Membrane Science, Vol. 423-424, p. 438-449 https://doi.org/10.1016/j.memsci.2012.08.045	journal	December 2012
Effect of Organic Cations on Hydrogen Oxidation Reaction of Carbon Supported Platinum Chung, Hoon Taek; Choe, Yoong-Kee; Martinez, Ulises Journal of The Electrochemical Society, Vol. 163, Issue 14 https://doi.org/10.1149/2.0511614jes	journal	January 2016
A Method of Casting Sound Ingots of Thermoelectric Materials Borle, W. N.; Sharma, B. L. Journal of The Electrochemical Society, Vol. 113, Issue 3 https://doi.org/10.1149/1.2423942	journal	January 1966
Effect of Water on the Stability of Quaternary Ammonium Groups for Anion Exchange Membrane Fuel Cell Applications Dekel, Dario R.; Amar, Michal; Willdorf, Sapir Chemistry of Materials, Vol. 29, Issue 10 https://doi.org/10.1021/acs.chemmater.7b00958	journal	May 2017
Anion exchange membranes composed of perfluoroalkylene chains and ammonium-functionalized oligophenylenes Ono, Hideaki; Miyake, Junpei; Shimada, Shigehumi Journal of Materials Chemistry A, Vol. 3, Issue 43 https://doi.org/10.1039/C5TA06454F	journal	January 2015
Gas transport properties of polysulphones: 1. Role of symmetry of methyl group placement on bisphenol rings McHattie, J. S.; Koros, W. J.; Paul, D. R. Polymer, Vol. 32, Issue 5 https://doi.org/10.1016/0032-3861(91)90508-G	journal	January 1991
1,2,3-Triazolium-Based Poly(2,6-Dimethyl Phenylene Oxide) Copolymers as Anion Exchange Membranes Liu, Lei; He, Shuqing; Zhang, Shufang ACS Applied Materials & Interfaces, Vol. 8, Issue 7 https://doi.org/10.1021/acsami.5b11519	journal	February 2016
Fourier transform pulsed-gradient spin-echo studies of molecular diffusion Stilbs, Peter Progress in Nuclear Magnetic Resonance Spectroscopy, Vol. 19, Issue 1 https://doi.org/10.1016/0079-6565(87)80007-9	journal	January 1987
Alkaline Stability of Quaternized Diels–Alder Polyphenylenes Park, Eun Joo; Maurya, Sandip; Hibbs, Michael R. Macromolecules, Vol. 52, Issue 14 https://doi.org/10.1021/acs.macromol.9b00853	journal	July 2019
Sorption, Transport, and Structural Evidence for Enhanced Free Volume in Poly(4-methyl-2-pentyne)/Fumed Silica Nanocomposite Membranes Merkel, T. C.; Freeman, B. D.; Spontak, R. J. Chemistry of Materials, Vol. 15, Issue 1 https://doi.org/10.1021/cm020672j	journal	January 2003
Rational design of polyaromatic ionomers for alkaline membrane fuel cells with >1 W cm ⁻² power density Maurya, Sandip; Noh, Sangtaik; Matanovic, Ivana Energy & Environmental Science, Vol. 11, Issue 11 https://doi.org/10.1039/C8EE02192A	journal	January 2018
Importance of balancing membrane and electrode water in anion exchange membrane fuel cells Omasta, T. J.; Wang, L.; Peng, X. Journal of Power Sources, Vol. 375 https://doi.org/10.1016/j.jpowsour.2017.05.006	journal	January 2018
Pt–Ru catalyzed hydrogen oxidation in alkaline media: oxophilic effect or electronic effect? Wang, Ying; Wang, Gongwei; Li, Guangwei Energy & Environmental Science, Vol. 8, Issue 1 https://doi.org/10.1039/C4EE02564D	journal	January 2015
Gas transport properties of polysulphones: 2. Effect of bisphenol connector groups McHattie, J. S.; Koros, W. J.; Paul, D. R. Polymer, Vol. 32, Issue 14 https://doi.org/10.1016/0032-3861(91)90343-H	journal	January 1991
Alkaline polymer electrolyte fuel cells stably working at 80 °C Peng, Hanqing; Li, Qihao; Hu, Meixue Journal of Power Sources, Vol. 390 https://doi.org/10.1016/j.jpowsour.2018.04.047	journal	June 2018
Impact of ionomer adsorption on alkaline hydrogen oxidation activity and fuel cell performance Li, Dongguo; Chung, Hoon T.; Maurya, Sandip Current Opinion in Electrochemistry, Vol. 12 https://doi.org/10.1016/j.coelec.2018.11.012	journal	December 2018
Functionalization of Poly(2,6-dimethyl-1,4-phenylene oxide)s with Hindered Fluorene Side Chains for Anion Exchange Membranes Zhu, Liang; Pan, Jing; Christensen, Caroline M. Macromolecules, Vol. 49, Issue 9 https://doi.org/10.1021/acs.macromol.6b00578	journal	April 2016
Poly(aryl piperidinium) membranes and ionomers for hydroxide exchange membrane fuel cells Wang, Junhua; Zhao, Yun; Setzler, Brian P. Nature Energy, Vol. 4, Issue 5 https://doi.org/10.1038/s41560-019-0372-8	journal	April 2019
Benzene Adsorption: A Significant Inhibitor for the Hydrogen Oxidation Reaction in Alkaline Conditions Matanovic, Ivana; Chung, Hoon Taek; Kim, Yu Seung The Journal of Physical Chemistry Letters, Vol. 8, Issue 19 https://doi.org/10.1021/acs.jpclett.7b02228	journal	September 2017
Nuclear Relaxation of H ₂ and H ₂ @C ₆₀ in Organic Solvents Sartori, Elena; Ruzzi, Marco; Turro, Nicholas J. Journal of the American Chemical Society, Vol. 128, Issue 46 https://doi.org/10.1021/ja065172w	journal	November 2006
An optimised synthesis of high performance radiation-grafted anion-exchange membranes Wang, Lianqin; Magliocca, Emanuele; Cunningham, Emma L. Green Chemistry, Vol. 19, Issue 3 https://doi.org/10.1039/C6GC02526A	journal	January 2017
Alkaline quaternary ammonium hydroxides and their polymer electrolytes for electrochemical capacitors Gao, Han; Li, Jak; Lian, Keryn RSC Adv., Vol. 4, Issue 41 https://doi.org/10.1039/C4RA01014K	journal	January 2014
Phenyl Oxidation Impacts the Durability of Alkaline Membrane Water Electrolyzer Li, Dongguo; Matanovic, Ivana; Lee, Albert S. ACS Applied Materials & Interfaces, Vol. 11, Issue 10 https://doi.org/10.1021/acsami.9b00711	journal	February 2019
Cation–Hydroxide–Water Coadsorption Inhibits the Alkaline Hydrogen Oxidation Reaction Chung, Hoon Taek; Martinez, Ulises; Matanovic, Ivana The Journal of Physical Chemistry Letters, Vol. 7, Issue 22 https://doi.org/10.1021/acs.jpclett.6b02025	journal	October 2016
Surface enhanced spectroscopic investigations of adsorption of cations on electrochemical interfaces Dunwell, M.; Wang, Junhua; Yan, Y. Physical Chemistry Chemical Physics, Vol. 19, Issue 2 https://doi.org/10.1039/C6CP07207K	journal	January 2017
Sorption, swelling, and free volume of polybenzimidazole (PBI) and PBI/zeolitic imidazolate framework (ZIF-8) nano-composite membranes for pervaporation Shi, Gui Min; Chen, Hongmin; Jean, Y. C. Polymer, Vol. 54, Issue 2 https://doi.org/10.1016/j.polymer.2012.11.056	journal	January 2013
Anion exchange membranes with branched ionic clusters for fuel cells He, Yubin; Ge, Xiaolin; Liang, Xian Journal of Materials Chemistry A, Vol. 6, Issue 14 https://doi.org/10.1039/C8TA01114A	journal	January 2018
Anion exchange membrane fuel cells: Current status and remaining challenges Gottesfeld, Shimshon; Dekel, Dario R.; Page, Miles Journal of Power Sources, Vol. 375 https://doi.org/10.1016/j.jpowsour.2017.08.010	journal	January 2018
Toward Improved Alkaline Membrane Fuel Cell Performance Using Quaternized Aryl-Ether Free Polyaromatics Maurya, Sandip; Fujimoto, Cy H.; Hibbs, Michael R. Chemistry of Materials, Vol. 30, Issue 7 https://doi.org/10.1021/acs.chemmater.8b00358	journal	March 2018
N -Spirocyclic Quaternary Ammonium Ionenes for Anion-Exchange Membranes Pham, Thanh Huong; Olsson, Joel S.; Jannasch, Patric Journal of the American Chemical Society, Vol. 139, Issue 8 https://doi.org/10.1021/jacs.6b12944	journal	February 2017
Synthesis of Alkaline Anion Exchange Membranes with Chemically Stable Imidazolium Cations: Unexpected Cross-Linked Macrocycles from Ring-Fused ROMP Monomers You, Wei; Hugar, Kristina M.; Coates, Geoffrey W. Macromolecules, Vol. 51, Issue 8 https://doi.org/10.1021/acs.macromol.8b00209	journal	April 2018
Highly Conductive Anion-Exchange Membranes Based on Cross-Linked Poly(norbornene): Vinyl Addition Polymerization Mandal, Mrinmay; Huang, Garrett; Kohl, Paul A. ACS Applied Energy Materials, Vol. 2, Issue 4 https://doi.org/10.1021/acsaem.8b02051	journal	March 2019
A Microelectrode Study of Interfacial Reactions at the Platinum-Alkaline Polymer Interface Yim, Sung-Dae; Chung, Hoon T.; Chlistunoff, Jerzy Journal of The Electrochemical Society, Vol. 162, Issue 6 https://doi.org/10.1149/2.0151506jes	journal	January 2015
On the origin of permanent performance loss of anion exchange membrane fuel cells: Electrochemical oxidation of phenyl group Maurya, Sandip; Lee, Albert S.; Li, Dongguo Journal of Power Sources, Vol. 436 https://doi.org/10.1016/j.jpowsour.2019.226866	journal	October 2019

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