Structure and property optimization of perfluorinated short side chain membranes for hydrogen fuel cells using orientational stretching

Small-angle neutron scattering has been applied to study the structure peculiarities of perfluorinated proton conducting polymer samples containing sulfonic groups of the Aquivion® type in dry and moistened conditions, which differ from Nafion® type membranes by the length of the side chains with sulfonic acid groups. The fine structure of the membranes is revealed, which is based on a system of regular proton conducting channels in the perfluorinated polymer matrix. The way this fine structure changes was determined as a function of the equivalent weight of the membrane, and the relation of these changes with proton conductivity value is established. The neutron contrast variation method enabled us to study the effect of orientational stretching on the fine structure. It was found that stretching is accompanied by an increase in proton conductivity due to changes in the fine structure of the channel system. Our investigations confirm that a reduction in the side chain length affects the fine structure of the perfluorinated proton conducting membranes, which is accompanied by an improvement in their performance in hydrogen fuel cells. Therefore, Aquivion® type systems will allow to reduce and possibly remove the existing operational restrictions of Nafion®.

[1]  S. Kurtz,et al.  Morphology and Crystalline Architecture of Polyaryletherketones , 2019, PEEK Biomaterials Handbook.

[2]  S. Ivanchev,et al.  Optimization of the conditions of ethylene polymerization into reactor powders of ultra-high-molecular-weight polyethylene suitable for solid-phase formation into oriented ultra-high-strength and ultra-high-modulus film yarns , 2016, Doklady Physical Chemistry.

[3]  M. Rikukawa,et al.  Elucidation of the morphology of the hydrocarbon multi-block copolymer electrolyte membranes for proton exchange fuel cells , 2016 .

[4]  E. Andablo-Reyes,et al.  Aluminoxane co-catalysts for the activation of a bis phenoxyimine titanium (IV) catalyst in the synthesis of disentangled ultra-high molecular weight polyethylene , 2015 .

[5]  S. Ivanchev,et al.  Structure characterization of perfluorosulfonic short side chain polymer membranes , 2015 .

[6]  S. Ronca,et al.  Solvent-Free Solid-State-Processed Tapes of Ultrahigh-Molecular-Weight Polyethylene: Influence of Molar Mass and Molar Mass Distribution on the Tensile Properties , 2015 .

[7]  A. Yaroslavtsev.  Perfluorinated ion-exchange membranes , 2013, Polymer Science Series A.

[8]  A. Khokhlov,et al.  Large-scale atomistic and quantum-mechanical simulations of a Nafion membrane: Morphology, proton solvation and charge transport , 2013, Beilstein journal of nanotechnology.

[9]  D. Bihan,et al.  Effective diffusion tensor computed by homogenization , 2013 .

[10]  S. Ivanchev,et al.  Properties of oriented film tapes prepared via solid-state processing of a nascent ultrahigh-molecular-weight polyethylene reactor powder synthesized with a postmetallocene catalyst , 2012, Polymer Science Series A.

[11]  S. Ivanchev,et al.  Effect of preparation conditions on nanostructural features of the NAFION® type perfluorinated proton conducting membranes , 2012, Petroleum Chemistry.

[12]  V. G. Barabanov,et al.  Scientific principles of a new process for manufacturing perfluorinated polymer electrolytes for fuel cells , 2012, Petroleum Chemistry.

[13]  E. Roduner,et al.  Spatial distribution and dynamics of proton conductivity in fuel cell membranes: potential and limitations of electrochemical atomic force microscopy measurements , 2011, Journal of physics. Condensed matter : an Institute of Physics journal.

[14]  Jedeok Kim,et al.  Small-Angle X-ray Scattering and Proton Conductivity of Anhydrous Nafion-Blend Membranes for High Temperature PEFCs , 2009 .

[15]  S. Paddison,et al.  Effect of Molecular Weight on Hydrated Morphologies of the Short-Side-Chain Perfluorosulfonic Acid Membrane , 2009 .

[16]  E. Allahyarov,et al.  Simulation study of the correlation between structure and conductivity in stretched nafion. , 2008, The journal of physical chemistry. B.

[17]  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 .

[18]  A. Manthiram,et al.  Comparison of the small angle X-ray scattering study of sulfonated poly(etheretherketone) and Nafion membranes for direct methanol fuel cells , 2006 .

[19]  Zhiqing Shi,et al.  Structural Study of Proton-Conducting Fluorous Block Copolymer Membranes , 2006 .

[20]  V. Gordeliy,et al.  Scientific Reviews: Two-Detector System for Small-Angle Neutron Scattering Instrument , 2005 .

[21]  L. Rubatat,et al.  Orientation of Drawn Nafion at Molecular and Mesoscopic Scales , 2004 .

[22]  R. Weiss,et al.  The development of the ionic microphase in sulfonated poly(ethylene-co-propylene-co-ethylidene norbornene) ionomers during physical aging above Tg , 2002 .

[23]  J. Koberstein,et al.  Small-angle X-ray scattering studies of zinc stearate-filled sulfonated poly(ethylene-co-propylene-co-ethylidene norbornene) ionomers , 1999 .

[24]  D. I. Svergun,et al.  Structure Analysis by Small-Angle X-Ray and Neutron Scattering , 1987 .

[25]  J. Higgins,et al.  Small-angle neutron scattering from polypentenamer sulfonate ionomers , 1982 .

[26]  T. Russell,et al.  Small‐angle x‐ray scattering study of ionomer deformation , 1980 .

[27]  E. Roche,et al.  Small‐angle X‐ray and neutron scattering studies of the morphology of ionomers , 1980 .

[28]  S. Cooper,et al.  Morphology of Ionomers , 1973 .