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Title: The parameter space for scalable integration of atomically thin graphene with Nafion for proton exchange membrane (PEM) applications

Journal Article · · Materials Advances
DOI:https://doi.org/10.1039/D3MA00180F· OSTI ID:1992378
ORCiD logo [1];  [2]; ORCiD logo [3];  [4]; ORCiD logo [5]; ORCiD logo [6]
  1. Chemical and Biomolecular Engineering Department, Vanderbilt University, Nashville, TN, 37212, USA
  2. Chemical and Biomolecular Engineering Department, Vanderbilt University, Nashville, TN, 37212, USA, Interdisciplinary Graduate Program in Materials Science, Vanderbilt University, Nashville, TN, 37235, USA, Vanderbilt Institute of Nanoscale Science and Engineering, Nashville, TN, 37212, USA
  3. Department of Chemistry, Vanderbilt University, Nashville, TN, 37235, USA
  4. Interdisciplinary Graduate Program in Materials Science, Vanderbilt University, Nashville, TN, 37235, USA, Vanderbilt Institute of Nanoscale Science and Engineering, Nashville, TN, 37212, USA
  5. Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN, USA
  6. Chemical and Biomolecular Engineering Department, Vanderbilt University, Nashville, TN, 37212, USA, Interdisciplinary Graduate Program in Materials Science, Vanderbilt University, Nashville, TN, 37235, USA, Vanderbilt Institute of Nanoscale Science and Engineering, Nashville, TN, 37212, USA, Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN, USA, Mechanical Engineering Department, Vanderbilt University, Nashville, TN, 37212, USA

Selective proton permeation through atomically thin graphene while maintaining impermeability to even small gas atoms i.e. He or hydrated ions, presents potential for advancing proton exchange membranes (PEMs) across a range of energy conversion and storage applications. The incorporation of graphene into state-of-the-art proton conducting polymers e.g. Nafion can enable improvements in PEM selectivity as well as mitigate reactant crossover. The development of facile integration approaches are hence imperative. Here, we systematically study the parameters influencing the integration of monolayer graphene synthesized via scalable chemical vapor deposition (CVD) on polycrystalline Cu foils with a model proton conducting polymer (Nafion) via a facile hot-press process. The hot-press time (t), temperature (T) and pressure (P) are found to not only influence the quality of graphene transfer but can also introduce additional defects in the CVD graphene. Graphene transfers to Nafion performed below the optimum temperature (Topt ~ 115 °C) remain patchy with ruptures, while transfers above Topt showed defect features, and transfers near Topt show minimal ruptures and defect features. We demonstrate Nafion|graphene|Nafion sandwich membranes using the optimal transfer conditions that allow for ~50% reduction in hydrogen crossover (~0.17 mA cm–2) in comparison to Nafion control membranes (~0.33 mA cm–2) while maintaining comparable proton area specific resistance < 0.25 Ω cm2 (areal conductance ~ 4–5 S cm–2), that are adequate to enable practical PEM applications such as fuel cells, redox flow batteries, and beyond.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Vanderbilt Univ., Nashville, TN (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Office of Isotope R&D and Production (IRP); National Science Foundation (NSF)
Grant/Contract Number:
SC0022237; AC05-00OR22725; 1944134; SC0022915
OSTI ID:
1992378
Alternate ID(s):
OSTI ID: 1997611; OSTI ID: 2324831
Journal Information:
Materials Advances, Journal Name: Materials Advances Vol. 4 Journal Issue: 16; ISSN 2633-5409
Publisher:
Royal Society of Chemistry (RSC)Copyright Statement
Country of Publication:
United Kingdom
Language:
English

References (42)

Impermeable Atomic Membranes from Graphene Sheets journal August 2008
Fabrication of sub-nanometer pores on graphene membrane for ion selective transport journal January 2018
A monolayer graphene – Nafion sandwich membrane for direct methanol fuel cells journal April 2016
Raman spectroscopy of graphene on different substrates and influence of defects journal June 2008
Single-Layer Graphene Sandwiched between Proton-Exchange Membranes for Selective Proton Transmission journal January 2019
Effect of Different Hot-Pressing Pressure and Temperature on the Performance of Titanium Mesh-Based MEA for DMFC journal April 2022
High Hydrogen Isotope Separation Efficiency: Graphene or Catalyst? journal July 2022
Graphene enhances the proton selectivity of porous membrane in vanadium flow batteries journal January 2017
Deconstructing proton transport through atomically thin monolayer CVD graphene membranes journal January 2022
Glass Transition Temperature of Perfluorosulfonic Acid Ionomers journal May 2007
Direct transfer of graphene onto flexible substrates journal October 2013
State of Water in Disulfonated Poly(arylene ether sulfone) Copolymers and a Perfluorosulfonic Acid Copolymer (Nafion) and Its Effect on Physical and Electrochemical Properties journal August 2003
Facile Size-Selective Defect Sealing in Large-Area Atomically Thin Graphene Membranes for Sub-Nanometer Scale Separations journal July 2020
Proton transport through one-atom-thick crystals journal November 2014
Measuring the proton selectivity of graphene membranes journal November 2015
Electric Field Effect in Atomically Thin Carbon Films journal October 2004
Aqueous proton transfer across single-layer graphene journal March 2015
The Parameter Space of Graphene Chemical Vapor Deposition on Polycrystalline Cu journal October 2012
Nanoporous Atomically Thin Graphene Filters for Nanoscale Aerosols journal August 2022
Graphene-Based Proton Transmission and Hydrogen Crossover Mitigation in Electrochemical Hydrogen Pump Cells journal July 2019
Role of the glass transition temperature of Nafion 117 membrane in the preparation of the membrane electrode assembly in a direct methanol fuel cell (DMFC) journal September 2012
Importance of electrode hot-pressing conditions for the catalyst performance of proton exchange membrane fuel cells journal August 2015
Efficient Hydrogen Isotope Separation by Tunneling Effect Using Graphene-Based Heterogeneous Electrocatalysts in Electrochemical Hydrogen Isotope Pumping journal September 2022
2D Crystals Significantly Enhance the Performance of a Working Fuel Cell journal November 2016
Assessment and control of the impermeability of graphene for atomically thin membranes and barriers journal January 2017
Thermal Behavior of Nafion Membranes journal January 1999
Where is the glass transition temperature of poly(tetrafluoroethylene)? A new approach by dynamic rheometry and mechanical tests journal August 2013
Nanoporous Atomically Thin Graphene Membranes for Desalting and Dialysis Applications journal June 2017
Chemical vapor deposition of graphene on large-domain ultra-flat copper journal April 2014
Single-layer graphene as a highly selective barrier for vanadium crossover with high proton selectivity journal August 2021
Raman spectroscopy as a versatile tool for studying the properties of graphene journal April 2013
Facile Fabrication of Large-Area Atomically Thin Membranes by Direct Synthesis of Graphene with Nanoscale Porosity journal October 2018
Subatomic species transport through atomically thin membranes: Present and future applications journal November 2021
Experimental Studies of Graphene-Coated Polymer Electrolyte Membranes for Direct Methanol Fuel Cells journal December 2022
Scalable and efficient separation of hydrogen isotopes using graphene-based electrochemical pumping journal May 2017
NIH Image to ImageJ: 25 years of image analysis journal June 2012
Scalable synthesis of nanoporous atomically thin graphene membranes for dialysis and molecular separations via facile isopropanol-assisted hot lamination journal January 2021
Selective Proton/Deuteron Transport through Nafion|Graphene|Nafion Sandwich Structures at High Current Density journal January 2018
Ionic Conductance through Graphene: Assessing Its Applicability as a Proton Selective Membrane journal September 2019
Roll-to-roll production of 30-inch graphene films for transparent electrodes journal June 2010
Kinetic Control of Angstrom-Scale Porosity in 2D Lattices for Direct Scalable Synthesis of Atomically Thin Proton Exchange Membranes journal October 2022
Large scale atmospheric pressure chemical vapor deposition of graphene journal April 2013