Download or read book An Investigation of Structure property Relationships in Several Categories of Proton Exchange Membranes written by Marianne Phelan Rodgers and published by . This book was released on 2007 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: The chemical and structural features of proton exchange membranes (PEMs) are related to their fuel cell relevant properties. The objective of this work is to understand structure-property relationships in PEMs through the fabrication and characterization of several classes of membranes. Incorporation of linear and angled monomers into the main chain of a polyimide permitted investigation of the effect of kinked versus linear polymers on membrane properties. The conductivity of angled sulfonated polyimide membranes is greater than those prepared from linear polymers, but water uptakes are lower. These differences are attributed to increased entanglements of angled polymers, which limit the degree of swelling and lead to increased proton concentration. Polyelectrolytes were incorporated into reinforcing materials to study the effect of incorporating and confining polyelectrolytes in the pores of reinforcing materials. The employment of reinforcing materials reduces conductivity, mobility, and permeance due to decreased ionomer content and connectivity of the ionomer. However, membranes are stronger and thinner, which compensates for these losses in terms of lower resistance and increased dimensional stability. Incorporating zirconium hydrogen phosphate (ZrP) and silicon dioxide (SiO2) into Nafion℗ membranes permitted investigation of their effect on membrane properties. Data for Nafion℗/ZrP membranes support the theory that ZrP disrupts cohesive forces in Nafion℗, causing it to absorb more water. The increased water content of the membranes does not result in increased conductivity because there is a concurrent decrease in proton concentration and mobility due to poorly conducting ZrP disrupting the conduction pathway and increased water content diluting protons and separating proton conduction sites. The decreasing density of the Nafion℗/SiO2 composite membranes with increasing SiO2 content and the increased dimensional stability of the membranes increasing compared to unmodified Nafion℗ support the theory that a rigid scaffolding forms. Due to formation of void space that increases with increasing SiO2 content, water content increases, thus diluting the protons in the membrane, leading to lower conductivity. These structure-property relationships may be relevant to other membrane systems and should be considered when designing alternative systems for proton exchange membranes.
Download or read book Polymer Membranes for Fuel Cells written by Javaid Zaidi and published by Springer Science & Business Media. This book was released on 2010-07-15 with total page 439 pages. Available in PDF, EPUB and Kindle. Book excerpt: From the late-1960’s, perfluorosulfonic acid (PFSAs) ionomers have dominated the PEM fuel cell industry as the membrane material of choice. The “gold standard’ amongst the many variations that exist today has been, and to a great extent still is, DuPont’s Nafion® family of materials. However, there is significant concern in the industry that these materials will not meet the cost, performance, and durability requirementsnecessary to drive commercialization in key market segments – es- cially automotive. Indeed, Honda has already put fuel cell vehicles in the hands of real end users that have home-grown fuel cell stack technology incorporating hydrocarbon-based ionomers. “Polymer Membranes in Fuel Cells” takes an in-depth look at the new chem- tries and membrane technologies that have been developed over the years to address the concerns associated with the materials currently in use. Unlike the PFSAs, which were originally developed for the chlor-alkali industry, the more recent hydrocarbon and composite materials have been developed to meet the specific requirements of PEM Fuel Cells. Having said this, most of the work has been based on derivatives of known polymers, such as poly(ether-ether ketones), to ensure that the critical requirement of low cost is met. More aggressive operational requi- ments have also spurred the development on new materials; for example, the need for operation at higher temperature under low relative humidity has spawned the creation of a plethora of new polymers with potential application in PEM Fuel Cells.
Download or read book Examining Structure Property Relationships of Proton Exchange Membranes Through the Study of Model Sulfonated Graft Copolymers written by Ching-Ching Ami Yang and published by . This book was released on 2014 with total page 187 pages. Available in PDF, EPUB and Kindle. Book excerpt: The role of polymer nanostructure on morphology, crystallinity, water sorption and proton conductivity was investigated using a model solid polymer electrolyte. Poly([vinylidene difluoride-co-chlorotrifluoroethylene]-graft-styrene) [P(VDF-co-CTFE)-g-PS], which consists of a hydrophobic, fluorous backbone and styrenic graft chains of varied length was synthesized with controlled chain architecture and chemical composition. The polystyrene graft chains were sulfonated to different degrees to provide three series of polymers with controlled ion exchange capacity (IEC). Due to chemical dissimilarity of the hydrophobic fluorous segments and the hydrophilic sulfonated polystyrene segments, the copolymers phase separate into ionic and non-ionic domains. The ionic domains allow transport of water and protons; the hydrophobic domains provide mechanical integrity, preventing the membranes from dissolving in water. The design of the model graft copolymers allows systematic examination of the effects of graft length and graft density on water sorption and proton conductivity. One of the major features of this work is that the sulfonated graft copolymers with shortest graft chains exhibit highest degree of crystallinity and highest PVDF content, which restrict excessive swelling and alleviate acid dilution, leading to a wider IEC operating range for high proton conductivity. Furthermore, the short graft copolymers allow access to very high IEC membranes that are insoluble in water. These short graft polymers with high IECs exhibit exceptionally high proton conduction under reduced humidity and elevated temperatures. In addition, for a given PVDF content, the lower graft density copolymers were observed to possess higher crystallinity and more contiguous PVDF domains that allow high IEC membranes to be prepared that possess lower degrees of swelling. Another important finding is that blending fully sulfonated graft copolymers with high molecular weight PVDF yields membranes with overall low IECs that exhibit highly localized ion content. This promotes the interconnection of ionic domains for effective proton transport while the more extended hydrophobic domains significantly reduce excessive swelling which serve to maintain the mechanical property of the membranes. This thesis describes a systematic approach, demonstrating the design, synthesis, characterization of model polymers, followed by the analysis of structure-property relationships in proton exchange membranes.
Download or read book Structure property Relationships in Anion Exchange Membranes Containing Hydrogen Bonding Motifs written by Babak Sabetpour and published by . This book was released on 2019 with total page 62 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Dissertation Abstracts International written by and published by . This book was released on 2008 with total page 800 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Membranes for Electrochemical Applications written by J. Weidner and published by The Electrochemical Society. This book was released on 2008-04 with total page 69 pages. Available in PDF, EPUB and Kindle. Book excerpt: The papers included in this issue of ECS Transactions were originally presented in the symposium ¿Membranes for Electrochemical Applications¿, held during the 211th meeting of The Electrochemical Society, in Chicago, IL, from May 6 to 11, 2007.
Download or read book Water Hydrogen Bonding in Proton Exchange and Neutral Polymer Membranes written by Sarah Smedley and published by . This book was released on 2015 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Understanding the dynamics of water sorbed into polymer films is critical to reveal structure-property relationships in membranes for energy and water treatment applications, where membranes must interact with water to facilitate or inhibit the transport of ions. The chemical structure of the polymer has drastic effects on the transport properties of the membrane due to the morphological structure of the polymer and how water is interacting with the functional groups on the polymer backbone. Therefore studying the dynamics of water adsorbed into a membrane will give insight into how water-polymer interactions influence transport properties of the film. With a better understanding of how to design materials to have specific properties, we can accelerate development of smarter materials for both energy and water treatment applications to increase efficiency and create high-flux materials and processes. The goal of this dissertation is to investigate the water-polymer interactions in proton exchange and uncharged membranes and make correlations to their charge densities and transport properties. A linear Fourier Transform Infrared (FTIR) spectroscopic method for measuring the hydrogen bonding distribution of water sorbed in proton exchange membranes is described in this thesis. The information on the distribution of the microenvironments of water in an ionic polymer is critical to understanding the effects of different acidic groups on the proton conductivity of proton exchange membranes at low relative humidity. The OD stretch of dilute HOD in H2O is a single, well-defined vibrational band. When HOD in dilute H2O is sorbed into a proton exchange membrane, the OD stretch peak shifts based on the microenvironment that water encounters within the nanophase separated structure of the material. This peak shift is a signature of different hydrogen bonding populations within the membrane, which can be deconvoluted rigorously for dilute HOD in H2O compared to only qualitative observations that can be made with pure D2O or H2O. The theory and experimental practice of determining the hydrogen bonding distribution of water in a range of proton exchange membranes bearing aromatic sulfonate and perfluorosulfonate groups using this OD stretch technique is discussed. The OD stretch of dilute HOD in H2O absorbed in a series of sulfonated syndiotactic poly(styrene) and sulfonated poly(sulfone) membranes was studied using FTIR spectroscopy to measure how the character of the sulfonate headgroup and the backbone polarity influenced the water-membrane interactions. Using a three-state model, the OD stretch yielded information about the populations of absorbed water participating in hydrogen bonds with polymer-tethered sulfonate groups, water in an intermediate state, or water hydrogen bonding with other water molecules. The perflouroalkyl sulfonate moiety, which behaves as a superacid, consistently displayed the largest fraction of headgroup-associated water due to its strong acidic character. Measurements of the OD stretch gave insight to the strength of the hydrogen bonds formed between water and the sulfonate groups. Water associated with the superacid displayed an OD stretch peak position that was blueshifted by 39 cm-1 compared to the aryl sulfonate associated water with an OD stretching frequency that was centered at 2547 cm-1. The polarity of the polymer backbone also affected the OD stretch peak position. As hydration increased, the OD peak stretching frequency in poly(styrene)-based membranes displayed a redshift from 2566 cm-1 to 2553 cm-1, whereas there was no OD peak maxima shift in poly(sulfone)-based membranes due to the greater amount of intermediate water in the more polar poly(sulfone) backbone system.To further understand how the acidity of the sulfonate can be altered and how the acidity affects the hydrogen bonding network of water in a polymer membrane, various polymers with small chemical differences in the perfluorosulfonate sidechain were studied. In addition to the vibrational spectroscopy measurements using HOD as a probe, the partial charges of the sulfonate groups were calculating using DMol3 DFT calculations. The calculations and the experimentally determined peak position of the OD stretch both correlated to give a ranking of acidity for the various sidechains. It was found that having a thioether linkage instead of an ether linkage (typical linkage for perflurosulfonates) increased the acidity of the sulfonate group due to the capability of sulfur to expand its octet and more readily accept additional electron density. Through DFT geometry optimization, it was discovered that the thioether linkage prefers a kinked configuration while the ether linkage gives a more linear sidechain structure. This structural configuration correlated to experimental findings allowing more water to interact with the sulfonate group containing the ether linkage than the thioether linkage due to the sulfonate group being more easily accessible, even though the thioether sidechain is more acidic.Three sulfonated poly(arylene sulfone) based polymers were studied using FTIR and DFT calculations to better understand how the acidity of the sulfonate groups were affected by the placement on the backbone. By increasing the number of sulfone groups, which have electron withdrawing properties, flanking the sulfonated aromatic ring, the acidity was increased. The charge density of a sulfonate group flanked by two sulfone groups was -1.626 (in units of fundamental charge), while the charge density of a sulfonate group flanked by one sulfone group increased to -1.703. Additionally, if the subsequent ring was unsulfonated, the charge density further increased to 1.737, indicating that some stability is gained by both available rings being sulfonated. The differences in charge density are reflected in the water uptake and conductivity measurements, where the samples with the lowest charge density had the highest water uptake and conductivity. The deconvoluted OD peak revealed that the sample with two sulfone groups flanking the sulfonated aromatic ring contains the highest amount of bulk-like water, which led to the increased conductivity. The polyamide active layer of commercially available reverse osmosis membranes was studied at various relative humilities to better understand how the structure of the active layer changes when hydrated. The fingerprint region was used to analyze changes in the vibrational signature of specific functional groups and to understand how different chemical moieties interact with water. Using the difference spectrum, the water-polymer interactions could be quantified and correlated to transport properties of the membrane. Increasing the amount of free carboxylic acid groups on the backbone will lead to an active layer that is less crosslinked and contains a greater number of larger pores, which results in a higher flux. Active layers that contained a smaller concentration of free carboxylic acids were more highly crosslinked and had a higher amount of smaller pores, resulting in a lower flux. In summary, by studying the water hydrogen bonding network in various proton exchange membranes and neutral polyamide membranes, a new understanding of structure-property relationships has been developed. This will lead to a greater understanding of transport properties and conductivity in various polymer membranes. Expanding this fundamental knowledge will lead to the development of smarter materials for energy and reverse osmosis applications, and the ideas developed here can be extended to new types of materials used for various needs.
Download or read book Structure property Relationships in Anion Exchange Membranes for Electrochemical Energy Conversion and Storage written by Christopher George Arges and published by . This book was released on 2013 with total page 614 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Proton Exchange Membrane Fuel Cells written by David P. Wilkinson and published by CRC Press. This book was released on 2009-11-24 with total page 462 pages. Available in PDF, EPUB and Kindle. Book excerpt: A Detailed, Up-to-Date Treatment of Key Developments in PEMFC MaterialsThe potential to revolutionize the way we power our worldBecause of its lower temperature and special polymer electrolyte membrane, the proton exchange membrane fuel cell (PEMFC) is well-suited for transportation, portable, and micro fuel cell applications. But the performance o
Download or read book PEM Electrolysis for Hydrogen Production written by Dmitri Bessarabov and published by CRC Press. This book was released on 2016-02-03 with total page 401 pages. Available in PDF, EPUB and Kindle. Book excerpt: An ever-increasing dependence on green energy has brought on a renewed interest in polymer electrolyte membrane (PEM) electrolysis as a viable solution for hydrogen production. While alkaline water electrolyzers have been used in the production of hydrogen for many years, there are certain advantages associated with PEM electrolysis and its relevan
Download or read book Polymer Science A Comprehensive Reference written by and published by Newnes. This book was released on 2012-12-05 with total page 7752 pages. Available in PDF, EPUB and Kindle. Book excerpt: The progress in polymer science is revealed in the chapters of Polymer Science: A Comprehensive Reference, Ten Volume Set. In Volume 1, this is reflected in the improved understanding of the properties of polymers in solution, in bulk and in confined situations such as in thin films. Volume 2 addresses new characterization techniques, such as high resolution optical microscopy, scanning probe microscopy and other procedures for surface and interface characterization. Volume 3 presents the great progress achieved in precise synthetic polymerization techniques for vinyl monomers to control macromolecular architecture: the development of metallocene and post-metallocene catalysis for olefin polymerization, new ionic polymerization procedures, and atom transfer radical polymerization, nitroxide mediated polymerization, and reversible addition-fragmentation chain transfer systems as the most often used controlled/living radical polymerization methods. Volume 4 is devoted to kinetics, mechanisms and applications of ring opening polymerization of heterocyclic monomers and cycloolefins (ROMP), as well as to various less common polymerization techniques. Polycondensation and non-chain polymerizations, including dendrimer synthesis and various "click" procedures, are covered in Volume 5. Volume 6 focuses on several aspects of controlled macromolecular architectures and soft nano-objects including hybrids and bioconjugates. Many of the achievements would have not been possible without new characterization techniques like AFM that allowed direct imaging of single molecules and nano-objects with a precision available only recently. An entirely new aspect in polymer science is based on the combination of bottom-up methods such as polymer synthesis and molecularly programmed self-assembly with top-down structuring such as lithography and surface templating, as presented in Volume 7. It encompasses polymer and nanoparticle assembly in bulk and under confined conditions or influenced by an external field, including thin films, inorganic-organic hybrids, or nanofibers. Volume 8 expands these concepts focusing on applications in advanced technologies, e.g. in electronic industry and centers on combination with top down approach and functional properties like conductivity. Another type of functionality that is of rapidly increasing importance in polymer science is introduced in volume 9. It deals with various aspects of polymers in biology and medicine, including the response of living cells and tissue to the contact with biofunctional particles and surfaces. The last volume is devoted to the scope and potential provided by environmentally benign and green polymers, as well as energy-related polymers. They discuss new technologies needed for a sustainable economy in our world of limited resources. Provides broad and in-depth coverage of all aspects of polymer science from synthesis/polymerization, properties, and characterization methods and techniques to nanostructures, sustainability and energy, and biomedical uses of polymers Provides a definitive source for those entering or researching in this area by integrating the multidisciplinary aspects of the science into one unique, up-to-date reference work Electronic version has complete cross-referencing and multi-media components Volume editors are world experts in their field (including a Nobel Prize winner)
Download or read book Membrane Technology written by Sundergopal Sridhar and published by CRC Press. This book was released on 2018-09-03 with total page 541 pages. Available in PDF, EPUB and Kindle. Book excerpt: Contributed by multiple experts, the book covers the scientific and engineering aspects of membrane processes and systems. It aims to cover basic concepts of novel membrane processes including membrane bioreactors, microbial fuel cell, forward osmosis, electro-dialysis and membrane contactors. Maintains a pragmatic approach involving design, operation and cost analysis of pilot plants as well as scaled-up counterparts
Download or read book Advanced Materials for PEM Based Fuel Cell Systems written by James E. McGrath and published by . This book was released on 2005 with total page 516 pages. Available in PDF, EPUB and Kindle. Book excerpt: Proton exchange membrane fuel cells (PEMFCs) are quickly becoming attractive alternative energy sources for transportation, stationary power, and small electronics due to the increasing cost and environmental hazards of traditional fossil fuels. Two main classes of PEMFCs include hydrogen/air or hydrogen/oxygen fuel cells and direct methanol fuel cells (DMFCs). The current benchmark membrane for both types of PEMFCs is Nafion, a perfluorinated sulfonated copolymer made by DuPont. Nafion copolymers exhibit good thermal and chemical stability, as well as very high proton conductivity under hydrated conditions at temperatures below 80 degrees C. However, application of these membranes is limited due to their high methanol permeability and loss of conductivity at high temperatures and low relative humidities. These deficiencies have led to the search for improved materials for proton exchange membranes. Potential PEMs should have good thermal, hydrolytic, and oxidative stability, high proton conductivity, selective permeability, and mechanical durability over long periods of time. Poly(arylene ether)s, polyimides, polybenzimidazoles, and polyphenylenes are among the most widely investigated candidates for PEMs. Poly(arylene ether)s are a promising class of proton exchange membranes due to their excellent thermal and chemical stability and high glass transition temperatures. High proton conductivity can be achieved through post-sulfonation of poly(arylene ether) materials, but this most often results in very high water sorption or even water solubility. Our research has shown that directly polymerized poly(arylene ether) copolymers show important advantages over traditional post-sulfonated systems and also address the concerns with Nafion membranes. These properties were evaluated and correlated with morphology, structure-property relationships, and states of water in the membranes. Further improvements in properties were achieved through incorporation of inorganic fillers, such as phosphotungstic acid and zirconium hydrogen phosphate. Block copolymers were also studied due to the possibility to achieve a desired combination of homopolymer properties as well as the unique morphologies that are possible with block copolymers. Bezoyl substituted poly(p-phenylene) blocks were combined with poly(arylene ether) blocks to merge the structural rigidity of the poly(p-phenylene) with the ductility and high protonic conductivity of the poly(arylene ether)s. As evidenced by our many refereed publications and preprints, the research that we have conducted over the past several years has made a valuable and significant contribution to the literature and to the state of understanding of proton exchange membranes. Our early efforts at scale-up have suggested that the directly polymerized disulfonated poly(arylene ether sulfone) copolymers are commercially viable alternatives for proton exchange membranes. A new process for bipolar plates was developed and is described. An important single domain PEMFC model was developed and is documented in herein.
Download or read book PEM Fuel Cells written by Gurbinder Kaur and published by Elsevier. This book was released on 2021-11-16 with total page 584 pages. Available in PDF, EPUB and Kindle. Book excerpt: PEM Fuel Cells: Fundamentals, Advanced Technologies, and Practical Application provides a comprehensive introduction to the principles of PEM fuel cell, their working condition and application, and the latest breakthroughs and challenges for fuel cell technology. Each chapter follows a systematic and consistent structure with clear illustrations and diagrams for easy understanding. The opening chapters address the basics of PEM technology; stacking and membrane electrode assembly for PEM, degradation mechanisms of electrocatalysts, platinum dissolution and redeposition, carbon-support corrosion, bipolar plates and carbon nanotubes for the PEM, and gas diffusion layers. Thermodynamics, operating conditions, and electrochemistry address fuel cell efficiency and the fundamental workings of the PEM. Instruments and techniques for testing and diagnosis are then presented alongside practical tests. Dedicated chapters explain how to use MATLAB and COMSOL to conduct simulation and modeling of catalysts, gas diffusion layers, assembly, and membrane. Degradation and failure modes are discussed in detail, providing strategies and protocols for mitigation. High-temperature PEMs are also examined, as are the fundamentals of EIS. Critically, the environmental impact and life cycle of the production and storage of hydrogen are addressed, as are the risk and durability issues of PEMFC technology. Dedicated chapters are presented on the economics and commercialization of PEMFCs, including discussion of installation costs, initial capital costs, and the regulatory frameworks; apart from this, there is a separate chapter on their application to the automotive industry. Finally, future challenges and applications are considered. PEM Fuel Cells: Fundamentals, Advanced Technologies, and Practical Application provides an in-depth and comprehensive reference on every aspect of PEM fuel cells fundamentals, ideal for researchers, graduates, and students. Presents the fundamentals of PEM fuel cell technology, electrolytes, membranes, modeling, conductivity, recent trends, and future applications Addresses commercialization, public policy, and the environmental impacts of PEMFC in dedicated chapters Presents state-of-the-art PEMFC research alongside the underlying concepts
Download or read book Investigation on Structure and Behaviours of Proton Exchange Membrane Materials by TEM written by Zhe Wang and published by . This book was released on 2012 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Investigation on Structure and Behaviours of Proton Exchange Membrane Materials by TEM.
Download or read book Advanced Materials for PEM Based Fuel Cell Systems written by and published by . This book was released on 2005 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Proton exchange membrane fuel cells (PEMFCs) are quickly becoming attractive alternative energy sources for transportation, stationary power, and small electronics due to the increasing cost and environmental hazards of traditional fossil fuels. Two main classes of PEMFCs include hydrogen/air or hydrogen/oxygen fuel cells and direct methanol fuel cells (DMFCs). The current benchmark membrane for both types of PEMFCs is Nafion, a perfluorinated sulfonated copolymer made by DuPont. Nafion copolymers exhibit good thermal and chemical stability, as well as very high proton conductivity under hydrated conditions at temperatures below 80 à  à  à  à  à  à  à  à  à  à  à  à  à  à  à  à °C. However, application of these membranes is limited due to their high methanol permeability and loss of conductivity at high temperatures and low relative humidities. These deficiencies have led to the search for improved materials for proton exchange membranes. Potential PEMs should have good thermal, hydrolytic, and oxidative stability, high proton conductivity, selective permeability, and mechanical durability over long periods of time. Poly(arylene ether)s, polyimides, polybenzimidazoles, and polyphenylenes are among the most widely investigated candidates for PEMs. Poly(arylene ether)s are a promising class of proton exchange membranes due to their excellent thermal and chemical stability and high glass transition temperatures. High proton conductivity can be achieved through post-sulfonation of poly(arylene ether) materials, but this most often results in very high water sorption or even water solubility. Our research has shown that directly polymerized poly(arylene ether) copolymers show important advantages over traditional post-sulfonated systems and also address the concerns with Nafion membranes. These properties were evaluated and correlated with morphology, structure-property relationships, and states of water in the membranes. Further improvements in properties were achieved through incorporation of inorganic fillers, such as phosphotungstic acid and zirconium hydrogen phosphate. Block copolymers were also studied due to the possibility to achieve a desired combination of homopolymer properties as well as the unique morphologies that are possible with block copolymers. Bezoyl substituted poly(p-phenylene) blocks were combined with poly(arylene ether) blocks to merge the structural rigidity of the poly(p-phenylene) with the ductility and high protonic conductivity of the poly(arylene ether)s. As evidenced by our many refereed publications and preprints, the research that we have conducted over the past several years has made a valuable and significant contribution to the literature and to the state of understanding of proton exchange membranes. Our early efforts at scale-up have suggested that the directly polymerized disulfonated poly(arylene ether sulfone) copolymers are commercially viable alternatives for proton exchange membranes. A new process for bipolar plates was developed and is described. An important single domain PEMFC model was developed and is documented in this final report.
Download or read book Scientific and Technical Aerospace Reports written by and published by . This book was released on 1995 with total page 704 pages. Available in PDF, EPUB and Kindle. Book excerpt:
