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

Abstract

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.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [2];  [2]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Rensselaer Polytechnic Inst., Troy, NY (United States)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE). Fuel Cell Technologies Program; USDOE
OSTI Identifier:
1764206
Alternate Identifier(s):
OSTI ID: 1571303
Report Number(s):
LA-UR-20-21325
Journal ID: ISSN 2050-7488
Grant/Contract Number:  
89233218CNA000001
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 7; Journal Issue: 43; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Energy Sciences

Citation Formats

Park, Eun Joo, Lee, Albert Sung Soo, Leonard, Daniel Philip, Li, Dongguo, Jeon, Jong Yeob, Bae, Chul Sung, and Kim, Yu Seung. How does a small structural change of anode ionomer make a big difference in alkaline membrane fuel cell performance?. United States: N. p., 2019. Web. doi:10.1039/c9ta10157h.
Park, Eun Joo, Lee, Albert Sung Soo, Leonard, Daniel Philip, Li, Dongguo, Jeon, Jong Yeob, Bae, Chul Sung, & Kim, Yu Seung. How does a small structural change of anode ionomer make a big difference in alkaline membrane fuel cell performance?. United States. https://doi.org/10.1039/c9ta10157h
Park, Eun Joo, Lee, Albert Sung Soo, Leonard, Daniel Philip, Li, Dongguo, Jeon, Jong Yeob, Bae, Chul Sung, and Kim, Yu Seung. Mon . "How does a small structural change of anode ionomer make a big difference in alkaline membrane fuel cell performance?". United States. https://doi.org/10.1039/c9ta10157h. https://www.osti.gov/servlets/purl/1764206.
@article{osti_1764206,
title = {How does a small structural change of anode ionomer make a big difference in alkaline membrane fuel cell performance?},
author = {Park, Eun Joo and Lee, Albert Sung Soo and Leonard, Daniel Philip and Li, Dongguo and Jeon, Jong Yeob and Bae, Chul Sung and Kim, Yu Seung},
abstractNote = {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.},
doi = {10.1039/c9ta10157h},
journal = {Journal of Materials Chemistry. A},
number = 43,
volume = 7,
place = {United States},
year = {Mon Oct 14 00:00:00 EDT 2019},
month = {Mon Oct 14 00:00:00 EDT 2019}
}

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Works referenced in this record:

A one-shot sequence for high-resolution diffusion-ordered spectroscopy
journal, January 2002

  • Pelta, Michelle D.; Morris, Gareth A.; Stchedroff, Marc J.
  • Magnetic Resonance in Chemistry, Vol. 40, Issue 13
  • DOI: 10.1002/mrc.1107

Preparation of radiation-grafted powders for use as anion exchange ionomers in alkaline polymer electrolyte fuel cells
journal, January 2014

  • Poynton, Simon D.; Slade, Robert C. T.; Omasta, Travis J.
  • J. Mater. Chem. A, Vol. 2, Issue 14
  • DOI: 10.1039/C4TA00558A

Robust Hydroxide Ion Conducting Poly(biphenyl alkylene)s for Alkaline Fuel Cell Membranes
journal, July 2015


Anion conducting multiblock copolymer membranes with partial fluorination and long head-group tethers
journal, January 2016

  • Liu, Lisha; Ahlfield, John; Tricker, Andrew
  • Journal of Materials Chemistry A, Vol. 4, Issue 41
  • DOI: 10.1039/C6TA06653D

Cationic Polyelectrolytes, Stable in 10 M KOH aq at 100 °C
journal, September 2017


Resonance Stabilized Perfluorinated Ionomers for Alkaline Membrane Fuel Cells
journal, September 2013

  • Kim, Dae Sik; Fujimoto, Cy H.; Hibbs, Michael R.
  • Macromolecules, Vol. 46, Issue 19, p. 7826-7833
  • DOI: 10.1021/ma401568f

Alkaline Stability of Quaternary Ammonium Cations for Alkaline Fuel Cell Membranes and Ionic Liquids
journal, November 2014


NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist
journal, May 2010

  • Fulmer, Gregory R.; Miller, Alexander J. M.; Sherden, Nathaniel H.
  • Organometallics, Vol. 29, Issue 9
  • DOI: 10.1021/om100106e

Determination of Molecular Self-Diffusion Coefficients Using Pulsed-Field-Gradient NMR: An Experiment for Undergraduate Physical Chemistry Laboratory
journal, March 2012

  • Harmon, Jennifer; Coffman, Cierra; Villarrial, Spring
  • Journal of Chemical Education, Vol. 89, Issue 6
  • DOI: 10.1021/ed200471k

Quaternized aryl ether-free polyaromatics for alkaline membrane fuel cells: synthesis, properties, and performance – a topical review
journal, January 2018

  • Park, Eun Joo; Kim, Yu Seung
  • Journal of Materials Chemistry A, Vol. 6, Issue 32
  • DOI: 10.1039/C8TA05428B

Synthesis of Aromatic Anion Exchange Membranes by Friedel–Crafts Bromoalkylation and Cross-Linking of Polystyrene Block Copolymers
journal, February 2019


An electron-beam-grafted ETFE alkaline anion-exchange membrane in metal-cation-free solid-state alkaline fuel cells
journal, May 2006


Precision Synthesis of Narrow Polydispersity, Ultrahigh Molecular Weight Linear Aromatic Polymers by A 2 + B 2 Nonstoichiometric Step-Selective Polymerization
journal, August 2012

  • Cruz, Alfredo R.; Hernandez, M. Carmen G.; Guzmán-Gutiérrez, Maria T.
  • Macromolecules, Vol. 45, Issue 17
  • DOI: 10.1021/ma301691f

Poly(terphenylene) Anion Exchange Membranes: The Effect of Backbone Structure on Morphology and Membrane Property
journal, April 2017


Adsorption of Polyaromatic Backbone Impacts the Performance of Anion Exchange Membrane Fuel Cells
journal, May 2019


Backbone stability of quaternized polyaromatics for alkaline membrane fuel cells
journal, December 2012


Effect of Organic Cations on Hydrogen Oxidation Reaction of Carbon Supported Platinum
journal, January 2016

  • Chung, Hoon Taek; Choe, Yoong-Kee; Martinez, Ulises
  • Journal of The Electrochemical Society, Vol. 163, Issue 14
  • DOI: 10.1149/2.0511614jes

A Method of Casting Sound Ingots of Thermoelectric Materials
journal, January 1966

  • Borle, W. N.; Sharma, B. L.
  • Journal of The Electrochemical Society, Vol. 113, Issue 3
  • DOI: 10.1149/1.2423942

Effect of Water on the Stability of Quaternary Ammonium Groups for Anion Exchange Membrane Fuel Cell Applications
journal, May 2017


Anion exchange membranes composed of perfluoroalkylene chains and ammonium-functionalized oligophenylenes
journal, January 2015

  • Ono, Hideaki; Miyake, Junpei; Shimada, Shigehumi
  • Journal of Materials Chemistry A, Vol. 3, Issue 43
  • DOI: 10.1039/C5TA06454F

Gas transport properties of polysulphones: 1. Role of symmetry of methyl group placement on bisphenol rings
journal, January 1991


1,2,3-Triazolium-Based Poly(2,6-Dimethyl Phenylene Oxide) Copolymers as Anion Exchange Membranes
journal, February 2016

  • Liu, Lei; He, Shuqing; Zhang, Shufang
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 7
  • DOI: 10.1021/acsami.5b11519

Fourier transform pulsed-gradient spin-echo studies of molecular diffusion
journal, January 1987


Alkaline Stability of Quaternized Diels–Alder Polyphenylenes
journal, July 2019


Sorption, Transport, and Structural Evidence for Enhanced Free Volume in Poly(4-methyl-2-pentyne)/Fumed Silica Nanocomposite Membranes
journal, January 2003

  • Merkel, T. C.; Freeman, B. D.; Spontak, R. J.
  • Chemistry of Materials, Vol. 15, Issue 1
  • DOI: 10.1021/cm020672j

Rational design of polyaromatic ionomers for alkaline membrane fuel cells with >1 W cm −2 power density
journal, January 2018

  • Maurya, Sandip; Noh, Sangtaik; Matanovic, Ivana
  • Energy & Environmental Science, Vol. 11, Issue 11
  • DOI: 10.1039/C8EE02192A

Importance of balancing membrane and electrode water in anion exchange membrane fuel cells
journal, January 2018


Pt–Ru catalyzed hydrogen oxidation in alkaline media: oxophilic effect or electronic effect?
journal, January 2015

  • Wang, Ying; Wang, Gongwei; Li, Guangwei
  • Energy & Environmental Science, Vol. 8, Issue 1
  • DOI: 10.1039/C4EE02564D

Gas transport properties of polysulphones: 2. Effect of bisphenol connector groups
journal, January 1991


Alkaline polymer electrolyte fuel cells stably working at 80 °C
journal, June 2018


Impact of ionomer adsorption on alkaline hydrogen oxidation activity and fuel cell performance
journal, December 2018


Functionalization of Poly(2,6-dimethyl-1,4-phenylene oxide)s with Hindered Fluorene Side Chains for Anion Exchange Membranes
journal, April 2016


Poly(aryl piperidinium) membranes and ionomers for hydroxide exchange membrane fuel cells
journal, April 2019


Benzene Adsorption: A Significant Inhibitor for the Hydrogen Oxidation Reaction in Alkaline Conditions
journal, September 2017

  • Matanovic, Ivana; Chung, Hoon Taek; Kim, Yu Seung
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 19
  • DOI: 10.1021/acs.jpclett.7b02228

Nuclear Relaxation of H 2 and H 2 @C 60 in Organic Solvents
journal, November 2006

  • Sartori, Elena; Ruzzi, Marco; Turro, Nicholas J.
  • Journal of the American Chemical Society, Vol. 128, Issue 46
  • DOI: 10.1021/ja065172w

An optimised synthesis of high performance radiation-grafted anion-exchange membranes
journal, January 2017

  • Wang, Lianqin; Magliocca, Emanuele; Cunningham, Emma L.
  • Green Chemistry, Vol. 19, Issue 3
  • DOI: 10.1039/C6GC02526A

Alkaline quaternary ammonium hydroxides and their polymer electrolytes for electrochemical capacitors
journal, January 2014


Phenyl Oxidation Impacts the Durability of Alkaline Membrane Water Electrolyzer
journal, February 2019

  • Li, Dongguo; Matanovic, Ivana; Lee, Albert S.
  • ACS Applied Materials & Interfaces, Vol. 11, Issue 10
  • DOI: 10.1021/acsami.9b00711

Cation–Hydroxide–Water Coadsorption Inhibits the Alkaline Hydrogen Oxidation Reaction
journal, October 2016

  • Chung, Hoon Taek; Martinez, Ulises; Matanovic, Ivana
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 22
  • DOI: 10.1021/acs.jpclett.6b02025

Surface enhanced spectroscopic investigations of adsorption of cations on electrochemical interfaces
journal, January 2017

  • Dunwell, M.; Wang, Junhua; Yan, Y.
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 2
  • DOI: 10.1039/C6CP07207K

Anion exchange membranes with branched ionic clusters for fuel cells
journal, January 2018

  • He, Yubin; Ge, Xiaolin; Liang, Xian
  • Journal of Materials Chemistry A, Vol. 6, Issue 14
  • DOI: 10.1039/C8TA01114A

Anion exchange membrane fuel cells: Current status and remaining challenges
journal, January 2018


Toward Improved Alkaline Membrane Fuel Cell Performance Using Quaternized Aryl-Ether Free Polyaromatics
journal, March 2018


N -Spirocyclic Quaternary Ammonium Ionenes for Anion-Exchange Membranes
journal, February 2017

  • Pham, Thanh Huong; Olsson, Joel S.; Jannasch, Patric
  • Journal of the American Chemical Society, Vol. 139, Issue 8
  • DOI: 10.1021/jacs.6b12944

Highly Conductive Anion-Exchange Membranes Based on Cross-Linked Poly(norbornene): Vinyl Addition Polymerization
journal, March 2019

  • Mandal, Mrinmay; Huang, Garrett; Kohl, Paul A.
  • ACS Applied Energy Materials, Vol. 2, Issue 4
  • DOI: 10.1021/acsaem.8b02051

A Microelectrode Study of Interfacial Reactions at the Platinum-Alkaline Polymer Interface
journal, January 2015

  • Yim, Sung-Dae; Chung, Hoon T.; Chlistunoff, Jerzy
  • Journal of The Electrochemical Society, Vol. 162, Issue 6
  • DOI: 10.1149/2.0151506jes

On the origin of permanent performance loss of anion exchange membrane fuel cells: Electrochemical oxidation of phenyl group
journal, October 2019