Membrane architecture with ion-conducting channels through swift heavy ion induced graft copolymerization

Proton exchange membranes (PEMs) are of interest as key elements in various electrochemical devices, such as fuel cells, electrolyzers or flow batteries. The structure of commonly used PEMs consists of a random arrangement of proton conducting domains, formed by phase separation of hydrophilic ionomer constituents from the hydrophobic polymer backbone. This paper presents an approach for the synthesis of polymer electrolytes with proton conducting domains aligned in the through-plane direction of the membrane, prepared via swift heavy ion (SHI) irradiation followed by graft copolymerization and sulfonation to introduce proton conducting motifs. This paper presents a comprehensive discussion of the effect of SHI irradiation on the structure and fuel cell relevant properties of a PEM including performance measurements at the device (cell) level. Membranes were synthesized with various densities of proton conducting channels, which were identified via elemental mapping and electrochemical AFM. These membranes showed superior proton conductivity compared to membranes prepared by standard electron-beam induced grafting.

[1]  F. Coms.  The Chemistry of Fuel Cell Membrane Chemical Degradation , 2008, ECS Transactions.

[2]  A. Weber,et al.  New Insights into Perfluorinated Sulfonic-Acid Ionomers. , 2017, Chemical reviews.

[3]  U. Gasser,et al.  Radiation Grafted Ion-Conducting Membranes: The Influence of Variations in Base Film Nanostructure , 2016 .

[4]  L. Gubler,et al.  Grafting Design: A Strategy to Increase the Performance of Radiation Grafted Membranes , 2016 .

[5]  B. Godin,et al.  Poly(4-vinyl pyridine) radiografted PVDF track etched membranes as sensors for monitoring trace mercury in water , 2016 .

[6]  D. Rana,et al.  A poly(vinylidene fluoride-co-hexafluoro propylene) nanohybrid membrane using swift heavy ion irradiation for fuel cell applications , 2015 .

[7]  Norishige Konno,et al.  Development of Compact and High-Performance Fuel Cell Stack , 2015 .

[8]  J. Kerres.  Design Concepts for Aromatic Ionomers and Ionomer Membranes to be Applied to Fuel Cells and Electrolysis , 2015 .

[9]  J. Smiatek,et al.  Proton Dissociation of Sulfonated Polysulfones: Influence of Molecular Structure and Conformation , 2015 .

[10]  A. Wokaun,et al.  Mass spectrometry to quantify and compare the gas barrier properties of radiation grafted membranes and Nafion , 2014 .

[11]  Mohamed Mahmoud Nasef,et al.  Radiation-grafted membranes for polymer electrolyte fuel cells: current trends and future directions. , 2014, Chemical reviews.

[12]  U. Gasser,et al.  Structure of the aqueous phase and its impact on the conductivity of graft copolymer ionomers at saturation , 2014 .

[13]  L. Gubler.  Polymer Design Strategies for Radiation‐Grafted Fuel Cell Membranes , 2014 .

[14]  S. Holdcroft,et al.  Controlling Water Content and Proton Conductivity through Copolymer Morphology , 2013 .

[15]  A. Wokaun,et al.  Quantitative analysis of carbon corrosion during fuel cell start-up and shut-down by anode purging , 2012 .

[16]  U. Gasser,et al.  Nano-scale morphology in graft copolymer proton-exchange membranes cross-linked with DIPB , 2011 .

[17]  Lorenz Gubler,et al.  Radical (HO•, H• and HOO•) Formation and Ionomer Degradation in Polymer Electrolyte Fuel Cells , 2011 .

[18]  Y. Elabd,et al.  Block Copolymers for Fuel Cells , 2011 .

[19]  Timothy J. Peckham,et al.  Structure‐Morphology‐Property Relationships of Non‐Perfluorinated Proton‐Conducting Membranes , 2010, Advanced materials.

[20]  K. Cooper.  Progress Toward Accurate Through-Plane Ion Transport Resistance Measurement of Thin Solid Electrolytes , 2010 .

[21]  Moon Jeong Park,et al.  Anisotropic Proton Conduction in Aligned Block Copolymer Electrolyte Membranes at Equilibrium with Humid Air , 2010 .

[22]  A. Morin,et al.  Ion track grafting: A way of producing low-cost and highly proton conductive membranes for fuel cell applications , 2010 .

[23]  Y. Maekawa,et al.  Preparation of PTFE-based fuel cell membranes by combining latent track formation technology with graft polymerization , 2009 .

[24]  Shulamith Schlick,et al.  Visualizing chemical reactions and crossover processes in a fuel cell inserted in the ESR resonator: detection by spin trapping of oxygen radicals, nafion-derived fragments, and hydrogen and deuterium atoms. , 2009, The journal of physical chemistry. B.

[25]  A. Wokaun,et al.  Cross-Linker Effect in ETFE-Based Radiation-Grafted Proton-Conducting Membranes II. Extended Fuel Cell Operation and Degradation Analysis , 2009 .

[26]  Ram Devanathan,et al.  Recent developments in proton exchange membranes for fuel cells , 2008 .

[27]  Timothy J. Peckham,et al.  Relationships of Acid and water content to proton transport in statistically sulfonated proton exchange membranes: variation of water content via control of relative humidity. , 2008, Journal of Physical Chemistry B.

[28]  Timothy J. Peckham,et al.  Structural and Morphological Features of Acid-Bearing Polymers for PEM Fuel Cells , 2008 .

[29]  S. Holdcroft,et al.  Considerations of macromolecular structure in the design of proton conducting polymer membranes: graft versus diblock polyelectrolytes. , 2007, Journal of the American Chemical Society.

[30]  Y. Maekawa,et al.  Anisotropic proton-conducting membranes prepared from swift heavy ion-beam irradiated ETFE films , 2007 .

[31]  Timothy J. Peckham,et al.  Main-chain, statistically sulfonated proton exchange membranes: the relationships of acid concentration and proton mobility to water content and their effect upon proton conductivity , 2007 .

[32]  H. Kubota,et al.  Proton Exchange Membranes for Fuel Cell Applications Prepared by Ion Track Technology , 2007 .

[33]  David P. Wilkinson,et al.  High temperature PEM fuel cells , 2006 .

[34]  Minoru Inaba,et al.  Gas crossover and membrane degradation in polymer electrolyte fuel cells , 2006 .

[35]  N. Betz,et al.  Submicroscopic pores grafted using the residual sites produced by swift heavy ions , 2005 .

[36]  Steven Holdcroft,et al.  Synthetic Strategies for Controlling the Morphology of Proton Conducting Polymer Membranes , 2005 .

[37]  Nikhil H. Jalani,et al.  Thermodynamics and Proton Transport in Nafion II. Proton Diffusion Mechanisms and Conductivity , 2005 .

[38]  N. Betz,et al.  Swift heavy ion induced graft polymerization in track etched membranes’ submicroscopic pores , 2004 .

[39]  M. Hickner,et al.  Alternative polymer systems for proton exchange membranes (PEMs). , 2004, Chemical reviews.

[40]  S. Paddison,et al.  Transport in proton conductors for fuel-cell applications: simulations, elementary reactions, and phenomenology. , 2004, Chemical reviews.

[41]  Thomas J. Schmidt,et al.  Performance and Durability of Membrane Electrode Assemblies Based on Radiation‐Grafted FEP‐g‐Polystyrene Membranes , 2004 .

[42]  T. Rager.  Parameter Study for the Pre‐Irradiation Grafting of Styrene/Divinylbenzene onto Poly(tetrafluoroethylene‐co‐hexafluoropropylene) from Isopropanol Solution , 2004 .

[43]  S. Holdcroft,et al.  Enhanced Conductivity in Morphologically Controlled Proton Exchange Membranes: Synthesis of Macromonomers by SFRP and Their Incorporation into Graft Polymers , 2002 .

[44]  P. Apel,et al.  Track etching technique in membrane technology , 2001 .

[45]  K. Kreuer.  On the development of proton conducting polymer membranes for hydrogen and methanol fuel cells , 2001 .

[46]  J. Maier,et al.  Proton and water transport in nano-separated polymer membranes , 2000 .

[47]  C. Baquey,et al.  Surface treatment of biomaterials by gamma and swift heavy ions grafting , 1999 .

[48]  C. Baquey,et al.  A FTIR and SEM study of PS radiation grafted fluoropolymers: influence of the nature of the ionizing radiation on the film structure , 1999 .

[49]  C. Trautmann,et al.  Track size and track structure in polymer irradiated by heavy ions , 1998 .

[50]  F. Rouais,et al.  Synthesis of biomaterials by swift heavy ion grafting: Preliminary results of haemocompatibility , 1997 .

[51]  R. Spohr,et al.  Novel Thin Film with Cylindrical Nanopores That Open and Close Depending on Temperature: First Successful Synthesis , 1996 .

[52]  N. Betz.  Ion track grafting , 1995 .

[53]  N. Betz,et al.  Swift heavy ion modification of polymers , 1995 .

[54]  G. Gebel,et al.  Structural study of polystyrene grafted in irradiated polyvinylidene fluoride thin films , 1995 .

[55]  W. Enge,et al.  Energy loss dependent transversal etching rates of heavy ion tracks in plastic , 1995 .

[56]  W. Enge.  On the question of nuclear track formation in plastic material , 1995 .

[57]  J. Duraud,et al.  Grafting of polystyrene in poly(vinylidene fluoride) films by means of energetic heavy ions , 1992 .

[58]  M. Toulemonde,et al.  Latent tracks induced by heavy ions in the GeV energy range: Results at GANIL , 1988 .

[59]  G. Blanford,et al.  Detection of Charged Particles by Polymer Grafting , 1973, Science.