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Studying the ORR activity of platinum-based electrocatalysts is an urgent task in the development of materials for proton-exchange membrane fuel cells. The catalytic ink composition and the formation technique of a thin layer at the RDE play a significant role in studying ORR activity. The use of a polymer ionomer in the catalytic ink provides viscosity as well as proton conductivity. Nafion is widely used as an ionomer for research both at the RDE and in the MEA. The search for ionomers is a priority task in the development of the MEA components to replace Nafion. The study also considers the possibility of using the LF4-SK polymer as an alternative ionomer. The comparative results on the composition and techniques of applying the catalytic layer using LF4-SK and Nafion ionomers are presented, and the influence of the catalytic ink composition on the electrochemical characteristics of commercial platinum–carbon catalysts and a highly efficient platinum catalyst based on an N-doped carbon support is assessed. [ABSTRACT FROM AUTHOR]

Most commercially available polymers are synthesized from compounds derived from petroleum, a finite resource. Because of this, there is a growing interest in the synthesis of new polymeric materials using renewable monomers. Following this concept, this work reports on the use of muconic acid as a renewable source for the development of new polyamides that can be used as proton-exchange membranes. Muconic acid was used as a comonomer in polycondensation reactions with 4,4′-(hexafluoroisopropylidene)bis(p-phenyleneoxy)dianiline, 2,5-diaminobencensulfonic acid, and 4,4′-diamino-2,2′-stilbenedisulfonic acid as comonomers in the synthesis of two new series of partially renewable aromatic–aliphatic polyamides, in which the degree of sulfonation was varied. Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (1H, 13C, and 19F-NMR) techniques were used to confirm the chemical structures of the new polyamides. It was also observed that the degree of sulfonation was proportional to the molar ratio of the diamines in the feed. Subsequently, membranes were prepared by casting, and a complete characterization was conducted to determine their decomposition temperature (Td), glass transition temperature (Tg), density (ρ), and other physical properties. In addition, water uptake (Wu), ion-exchange capacity (IEC), and proton conductivity (σp) were determined for these membranes. Electrochemical impedance spectroscopy (EIS) was used to determine the conductivity of the membranes. MUFASA34 exhibited a σp value equal to 9.89 mS·cm−1, being the highest conductivity of all the membranes synthesized in this study. [ABSTRACT FROM AUTHOR]

The optimized design of the catalyst layer (CL) plays a vital role in improving the performance of polymer electrolyte membrane fuel cells (PEMFCs). The need to improve transport and catalyst activity is especially important at low Pt loading, where local oxygen and ionic transport resistances decrease the performance due to an inevitable reduction in active catalyst sites. In this work, local oxygen and ionic transport are analyzed using direct numerical simulation on virtually reconstructed microstructures. Four morphologies are examined: (i) heterogeneous, (ii) uniform, (iii) uniform vertically-aligned, and (iv) meso-porous ionomer distributions. The results show that the local oxygen transport resistance can be significantly reduced, while maintaining good ionic conductivity, through the design of high porosity CLs ( ε ≃ 0.6–0.7) with low agglomerated ionomer morphologies. Ionomer coalescence into thick films can be effectively mitigated by increasing the uniformity of thin films and reducing the tortuosity of ionomer distribution (e.g., good ionomer interconnection in supports with a vertical arrangement). The local oxygen resistance can be further decreased by the use of blended ionomers with enhanced oxygen permeability and meso-porous ionomers with oxygen transport routes in both water and ionomer. In summary, achieving high performance at low Pt loading in next-generation CLs must be accomplished through a combination of high porosity, uniform and low tortuosity ionomer distribution, and oxygen transport through activated water. [ABSTRACT FROM AUTHOR]

This study focuses on the thermal properties and structural features of blends consisting of thermoplastic starch (TPS) and poly(ethylene-co-methacrylic acid) copolymer (EMAA) or its ionomer form (EMAA-54Na). The aim is to investigate how carboxylate functional groups of the ionomer form intervene in blends compatibility at the interface of the two materials and how this impacts their properties. Two series of blends (TPS/EMAA and TPS/EMAA-54Na) were produced with an internal mixer, with TPS compositions between 5 and 90 wt%. Thermogravimetry shows two main weight losses, indicating that TPS and the two copolymers are primarily immiscible. However, a small weight loss existing at intermediate degradation temperature between those of the two pristine components reveals specific interactions at the interface. At a mesoscale level, scanning electron microscopy confirmed thermogravimetry results and showed a two-phase domain morphology, with a phase inversion at around 80 wt% TPS, but also revealed a different surface appearance evolution between the two series. Fourier-transformed infrared spectroscopy analysis also revealed discrepancies in fingerprint between the two series of blends, analysed in terms of additional interactions in TPS/EMAA-54Na coming from the supplementary sodium neutralized carboxylate functions of the ionomer. [ABSTRACT FROM AUTHOR]

In the past, platinum–copper catalysts have proven to be highly active for the oxygen reduction reaction (ORR), but transferring the high activities measured in thin-film rotating disk electrodes (TF-RDEs) to high-performing membrane electrode assemblies (MEAs) has proven difficult due to stability issues during operation. High initial performance can be achieved. However, fast performance decay on a timescale of 24 h is induced by repeated voltage load steps with H2/air supplied. This performance decay is accelerated if high relative humidity (>60% RH) is set for a prolonged time and low voltages are applied during polarization. The reasons and possible solutions for this issue have been investigated by means of electrochemical impedance spectroscopy and distribution of relaxation time analysis (EIS–DRT). The affected electrochemical sub-processes have been identified by comparing the PtCu electrocatalyst with commercial Pt/C benchmark materials in homemade catalyst-coated membranes (CCMs). The proton transport resistance (Rpt) increased by a factor of ~2 compared to the benchmark materials. These results provide important insight into the challenges encountered with the de-alloyed PtCu/KB electrocatalyst during cell break-in and operation. This provides a basis for improvements in the catalysts' design and break-in procedures for the highly attractive PtCu/KB catalyst system. [ABSTRACT FROM AUTHOR]

Intelligent Eucommia ulmoides rubber (EUR) and ionomer Surlyn resin (SR) blends were prepared and studied in this manuscript. This is the first paper to combine EUR with SR to prepare blends with both the shape memory effect and self-healing capability. The mechanical, curing, thermal, shape memory and self-healing properties were studied by a universal testing machine, differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA), respectively. Experimental results showed that the increase in ionomer content not only improved mechanical and shape memory properties but also endowed the compounds with excellent self-healing ability under the appropriate environmental conditions. Notably, the self-healing efficiency of the composites reached 87.41%, which is much higher than the efficiency of other covalent cross-linking composites. Therefore, these novel shape memory and self-healing blends can expand the use of natural Eucommia ulmoides rubber, such as in special medical devices, sensors and actuators. [ABSTRACT FROM AUTHOR]

Self-healing polymers such as poly(ethylene-co-methacrylic acid) ionomers (PEMAA) can heal themselves immediately after a projectile puncture which in turn lowers environmental pollution from replacement. In this study, the thermal-mechanical properties and self-healing response of a library of 15 PEMAA copolymers were studied to understand the effects of the ionic content (Li, Na, Zn, Mg) and neutralization percentage (13 to 78%) on the results. Differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and tensile testing were used to study the thermo-mechanical properties of PEMAA copolymers while the self-healing response was studied using the projectile test. Puncture sites were observed using scanning electron microscopy (SEM) and the healing efficiency was quantitatively measured using the water leakage test. Five different self-healing responses were observed and correlated to ionic content and neutralization. At high neutralization, divalent neutralizing ions (Zn and Mg) that have stronger ionic interactions exhibited brittle responses during projectile testing. PEMAA samples neutralized with Mg and Li at low concentrations had a higher healing efficiency than PEMAA samples neutralized with Zn and Na at low neutralization. The PEMAA copolymers with higher tensile stress and two distinct peaks in the graph of loss factor versus temperature that indicate the presence of sufficient ionic aggregate clusters had improved healing efficiency. By increasing the neutralization percentage from 20% to 70%, the tensile strength and modulus of the samples increased and their self-healability generally increased. Among the investigated samples, the copolymer with ~50% neutralization by Li salt showed the highest healing efficiency (100%). Overall, the strength and elastic response required for successful self-healing responses in PEMAA copolymers are shown to be governed by the choice of ion and the amount of neutralization. [ABSTRACT FROM AUTHOR]

The electrical properties of carbon-based filler-embedded polymer nanocomposites are essential for various applications such as antistatic and electromagnetic interference (EMI) applications. In this study, the impact of additives (i.e., ethylene-co-acid-co-sodium acid copolymer-based ionomer and cyanuric acid) on the antistatic, mechanical, thermal, and rheological properties of extruded multiwalled carbon nanotube (MWCNT)/polyoxymethylene (POM) nanocomposites were systematically investigated. The effects of each additive and the combination of additives were examined. Despite a slight reduction in mechanical properties, the incorporation of ionomer (coating on CNTs) and/or cyanuric acid (π-π interaction between CNTs and cyanuric acid) into the POM/CNT nanocomposites improved the CNT dispersity in the POM matrix, thereby enhancing electrical properties such as the electrical conductivity (and surface resistance) and electrical conductivity monodispersity. The optimum composition for the highest electrical properties was determined to be POM/1.5 wt% CNT/3.0 wt% ionomer/0.5 wt% cyanuric acid. The nanocomposites with tunable electrical properties are sought after, especially for antistatic and EMI applications such as electronic device-fixing jigs. [ABSTRACT FROM AUTHOR]

The development of smart elastomeric materials with inherent self-repairing abilities after mechanical damage has important technological and scientific implications, particularly in regard to the durability and life cycle of rubber products. The interest in self-healing materials for automotive applications is rapidly growing along with the increasing importance of vehicle scratch quality and quantity. The creation of a reversible network by noncovalent ionic cross-linking in elastomer/rubber blends is an effective approach to generate the self-healing phenomenon, with reprocessing and recycling properties. In this work, thermoplastic vulcanizates (TPVs) were prepared using ethylene–propylene–diene (EPDM) polymers and high-acid-containing thermoplastic ionomers. Along with the general EPDM, maleic anhydride grafted EPDM (EPDM-g-MAH) was also used for the preparation of the TPVs. The strategy was based on a simple ionic crosslinking reaction between the carboxyl groups present in the ionomer and zinc oxide (ZnO), where the formation of reversible Zn2+ salt bondings exhibits the self-healing behavior. The heterogeneous blending of EPDM and ionomers was also used to investigate the thermal and mechanical properties of the TPVs. The experimental findings were further supported by the surface morphology of the fracture surfaces viewed using microscopy. The self-healing behavior of the TPVs has been identified by scratch resistance testing, where the EPDM-g-MAH TPVs showed excellent healing efficiency of the scratch surface. Therefore, this work provides an efficient approach to fabricate new ionically cross-linked thermoplastic vulcanizates with excellent mechanical and self-repairing properties for the skins of automotive interior door trims and instrument panel applications. [ABSTRACT FROM AUTHOR]

This study reports a new phenomenon whereby the ionic content of a random ionomer was increased by the introduction of a hydrophobic modifier. In the current study, the ionomer synthesized from the solution polymerization of the three vinyl monomers, which are polar hydrophobic monomers acrylonitrile (AN), glycidyl methacrylate (GMA), and ionic monomer potassium 3-sulfopropyl methacrylate (SPM), encountered an early phase separation problem when the ionic content exceeded a certain threshold value. However, the addition of a strongly hydrophobic monomer, 2,2,3,3-tetrafluoropropyl methacrylate (TFPM), during the copolymerization is able to restrain this phase separation trend, consequently allowing 50% more of SPM units to be incorporated and uniformly distributed in the ionomer and achieving a random copolymer chain. The ionic clustering of the SPM units, which is the cause for the phase separation, was reduced as a result. The resulting random ionomer was demonstrated to be a superior proton conducting material over its ternary originator. This is due to the fact that TFPM possesses acidic protons, which brings about an association of TFPM with SPM and GMA via hydrogen bonding. This study could impact the synthesis of random ionomers by free radical polymerization since monitoring ionic content and improving ionic unit distribution in ionomers are issues encountered in several industries (e.g., the healthcare industry). [ABSTRACT FROM AUTHOR]

This article describes the development of a high power density Direct Formate Fuel Cell (DFFC) fed with potassium formate (KCOOH). The membrane electrode assembly (MEA) contains no platinum metal. The cathode catalyst is FeCo/C combined with a commercial anion exchange membrane (AEM). To enhance the power output and energy efficiency we have employed a nanostructured Pd/C-CeO2 anode catalyst. The activity for the formate oxidation reaction (FOR) is enhanced when compared to a Pd/C catalyst with the same Pd loading. Fuel cell tests at 60 °C show a peak power density of almost 250 mW cm-2. The discharge energy (14 kJ), faradic efficiency (89%) and energy efficiency (46%) were determined for a single fuel charge (30 mL of 4 M KCOOH and 4 M KOH). Energy analysis demonstrates that removal of the expensive KOH electrolyte is essential for the future development of these devices. To compensate we apply for the first time a polymeric ionomer in the catalyst layer of the anode electrode. A homopolymer is synthesized by the radical polymerization of vinyl benzene chloride followed by amination with 1,4-diazabicyclo[2.2.2]octane (DABCO). The energy delivered, energy efficiency and fuel consumption efficiency of DFFCs fed with 4 M KCOOH are doubled with the use of the ionomer. [ABSTRACT FROM AUTHOR]

We have investigated the dispersion state of a perfluorosulfonated ionomer (PFSI; Nafion®) in aqueous dispersion and the effect of methanol (MeOH) added to the aqueous dispersion by small-angle X-ray scattering (SAXS) as well as static and dynamic light scattering (SLS and DLS, respectively). Although both electrostatic and hydrophobic interactions of PFSI are expected to be strong in the dispersions, SAXS profiles obtained were satisfactorily fitted by the spherical particle model of a bimodal molar mass distribution. The rod-like aggregate model proposed in previous papers was denied at least for the present PFSI dispersion. Although the SAXS profiles exhibited a weak peak and the auto-correlation functions of DLS showed a log-time decay by the "repulsive cage effect" due to the long-ranged electrostatic interaction among PFSI particles, the concentration dependence of SLS results was probably normal because the cancellation of the electrostatic and hydrophobic interactions. The addition of MeOH into the aqueous dispersion of PFSI weakened both the hydrophobic and electcrostatic interactions of PFSI, and it is rather difficult to classify whether MeOH is a good or poor solvent (dispersant) for PFSI. [ABSTRACT FROM AUTHOR]

The carboxylic acid proton and the lithium coordination environments for precise and random Li-neutralized polyethylene acrylic acid P(E-AA) ionomers were explored using high speed solid-state 1H and 7Li MAS NMR. While the 7Li NMR revealed only a single Li coordination environment, the chemical shift temperature variation was dependent on the precise or random nature of the P(E-AA) ionomer. The 1H MAS NMR revealed two different carboxylic acid proton environments in these materials. By utilizing 1H-7Li rotational echo double resonance (REDOR) MAS NMR experiments, it was demonstrated that the proton environments correspond to different average 1H-7Li distances, with the majority of the protonated carboxylic acids having a close through space contact with the Li. Molecular dynamics simulations suggest that the shortest 1H-7Li distance corresponds to un-neutralized carboxylic acids directly involved in the coordination environment of Li clusters. These solid-state NMR results show that heterogeneous structural motifs need to be included when developing descriptions of these ionomer materials. [ABSTRACT FROM AUTHOR]

Optimization of the ionomer materials in catalyst layers (CLs) which sometimes is overlooked has been equally crucial as selection of the membranes in membrane electrode assembly (MEA) for achieving a superior performance in proton exchange membrane fuel cells (PEMFCs). Four combinations of the MEAs composed of short-side-chain (SSC) and long-side-chain (LSC) perfluorosulfonic acid (PFSA) polymers as membrane and ionomer materials have been prepared and tested under various temperatures and humidity conditions, aiming to investigate the effects of different side chain polymer in membranes and CLs on fuel cell performance. It is discovered that SSC PFSA polymer used as membrane and ionomer in CL yields better fuel cell performance than LSC PFSA polymer, especially at high temperature and low RH conditions. The MEA with the SSC PFSA employed both as a membrane and as an ionomer in cathode CL demonstrates the best cell performance amongst the investigated MEAs. Furthermore, various electrochemical diagnoses have been applied to fundamentally understand the contributions of the different resistances to the overall cell performance. It is illustrated that the charge transfer resistance (Rct) made the greatest contribution to the overall cell resistance and then membrane resistance (Rm), implying that the use of the advanced ionomer in CL could lead to more noticeable improvement in cell performance than only the substitution as the membrane. [ABSTRACT FROM AUTHOR]

Optimization of the ionomer materials in catalyst layers (CLs) which sometimes is overlooked has been equally crucial as selection of the membranes in membrane electrode assembly (MEA) for achieving a superior performance in proton exchange membrane fuel cells (PEMFCs). Four combinations of the MEAs composed of short-side-chain (SSC) and long-side-chain (LSC) perfluorosulfonic acid (PFSA) polymers as membrane and ionomer materials have been prepared and tested under various temperatures and humidity conditions, aiming to investigate the effects of different side chain polymer in membranes and CLs on fuel cell performance. It is discovered that SSC PFSA polymer used as membrane and ionomer in CL yields better fuel cell performance than LSC PFSA polymer, especially at high temperature and low RH conditions. The MEA with the SSC PFSA employed both as a membrane and as an ionomer in cathode CL demonstrates the best cell performance amongst the investigated MEAs. Furthermore, various electrochemical diagnoses have been applied to fundamentally understand the contributions of the different resistances to the overall cell performance. It is illustrated that the charge transfer resistance (R ct ) made the greatest contribution to the overall cell resistance and then membrane resistance (R m ), implying that the use of the advanced ionomer in CL could lead to more noticeable improvement in cell performance than only the substitution as the membrane.

Perfluorosulfonated ionomers are the most successful ion-exchange membranes at an industrial scale. One recent, cutting-edge application of perfluorosulfonated ionomers is in polymer electrolyte fuel cells (PEFCs). In PEFCs, the ionomers are used as a component of the catalyst layer (CL) in addition to functioning as a proton-exchange membrane. In this study, the microstructures in the CLs of PEFCs were characterized by combined synchrotron X-ray scattering and transmission electron microscopy (TEM) analyses. The CL comprised a catalyst, a support, and an ionomer. Fractal dimensional analysis of the combined ultrasmall- and small-angle X-ray scattering profiles indicated that the carbon-black-supported Pt catalyst (Pt/CB) surface was covered with the ionomer in the CL. Anomalous X-ray scattering revealed that the Pt catalyst nanoparticles on the carbon surfaces were aggregated in the CLs. These findings are consistent with the ionomer/catalyst microstructures and ionomer coverage on the Pt/CB surface obtained from TEM observations. [ABSTRACT FROM AUTHOR]

Proton-conducting ionomers are widespread materials for application in electrochemical energy storage devices. However, their properties depend strongly on operating conditions. In bio-fuel cells with a separator membrane, the swelling behavior as well as the conductivity need to be optimized with regard to the use of buffer solutions for the stability of the enzyme catalyst. This work presents a study of the hydrolytic stability, conductivity and mechanical behavior of different proton exchange membranes based on sulfonated poly(ether ether ketone) (SPEEK) and sulfonated poly(phenyl sulfone) (SPPSU) ionomers in phosphate buffer solution. The results show that the membrane stability can be adapted by changing the casting solvent (DMSO, water or ethanol) and procedures, including a crosslinking heat treatment, or by blending the two ionomers. A comparison with NafionTM shows the different behavior of this ionomer versus SPEEK membranes. [ABSTRACT FROM AUTHOR]

Tandem photo-electro-chemical cells composed of an assembly of a solid electrolyte membrane and two low-cost photoelectrodes have been developed to generate green solar fuel from water-splitting. In this regard, an anion-exchange polymer–electrolyte membrane, able to separate H2 evolved at the photocathode from O2 at the photoanode, was investigated in terms of ionic conductivity, corrosion mitigation, and light transmission for a tandem photo-electro-chemical configuration. The designed anionic membranes, based on polysulfone polymer, contained positive fixed functionalities on the side chains of the polymeric network, particularly quaternary ammonium species counterbalanced by hydroxide anions. The membrane was first investigated in alkaline solution, KOH or NaOH at different concentrations, to optimize the ion-exchange process. Exchange in 1M KOH solution provided high conversion of the groups, a high ion-exchange capacity (IEC) value of 1.59 meq/g and a hydroxide conductivity of 25 mS/cm at 60 °C for anionic membrane. Another important characteristic, verified for hydroxide membrane, was its transparency above 600 nm, thus making it a good candidate for tandem cell applications in which the illuminated photoanode absorbs the highest-energy photons (< 600 nm), and photocathode absorbs the lowest-energy photons. Furthermore, hydrogen crossover tests showed a permeation of H2 through the membrane of less than 0.1%. Finally, low-cost tandem photo-electro-chemical cells, formed by titanium-doped hematite and ionomer at the photoanode and cupric oxide and ionomer at the photocathode, separated by a solid membrane in OH form, were assembled to optimize the influence of ionomer-loading dispersion. Maximum enthalpy (1.7%), throughput (2.9%), and Gibbs energy efficiencies (1.3%) were reached by using n-propanol/ethanol (1:1 wt.) as solvent for ionomer dispersion and with a 25 µL cm−2 ionomer loading for both the photoanode and the photocathode. [ABSTRACT FROM AUTHOR]

Poly(tetrafluoroethylene) (PTFE) porous substrate-reinforced composite membranes for energy conversion technologies are prepared and characterized. In particular, we develop a new hydrophilic treatment method by in-situ biomimetic silicification for PTFE substrates having high porosity (60–80%) since it is difficult to impregnate ionomer into strongly hydrophobic PTFE porous substrates for the preparation of composite membranes. The thinner substrate having ~5 μm treated by the gallic acid/(3-trimethoxysilylpropyl)diethylenetriamine solution with the incubation time of 30 min shows the best hydrophilic treatment result in terms of contact angle. In addition, the composite membranes using the porous substrates show the highest proton conductivity and the lowest water uptake and swelling ratio. Membrane-electrode assemblies (MEAs) using the composite membranes (thinner and lower proton conductivity) and Nafion 212 (thicker and higher proton conductivity), which have similar areal resistance, are compared in I–V polarization curves. The I–V polarization curves of two MEAs in activation and Ohmic region are very identical. However, higher mass transport limitation is observed for Nafion 212 since the composite membrane with less thickness than Nafion 212 would result in higher back diffusion of water and mitigate cathode flooding. [ABSTRACT FROM AUTHOR]

Polymer electrolyte fuel cells with alkaline anion exchange membranes (AAEMs) have gained increasing attention because of the faster reaction kinetics associated with the alkaline environment compared to acidic media. While the development of anion exchange polymer membranes is increasing, the catalytic layer structure and composition of electrodes is of paramount importance to maximize fuel cell performance. In this work, we examine the preparation procedures for electrodes by catalyst-coated substrate to be used with a well-known commercial AAEM, Fumasep® FAA-3, and a commercial ionomer of the same nature (Fumion), both from Fumatech GmbH. The anion exchange procedure, the ionomer concentration in the catalytic layer and also the effect of membrane thickness, are investigated as they are very relevant parameters conditioning the cell behavior. The best power density was achieved upon ion exchange of the ionomer by submerging the electrodes in KCl (isopropyl alcohol/water solution) for at least one hour, two exchange steps, followed by treatment in KOH for 30 min. The optimum ionomer (Fumion) concentration was found to be close to 50 wt%, with a relatively narrow interval of functioning ionomer percentages. These results provide a practical guide for electrode preparation in AAEM-based fuel cell research. [ABSTRACT FROM AUTHOR]

Theoretical models used to describe the proton-conductive membrane in polymer electrolyte membrane fuel cells (PEMFCs) are reviewed, within the specific context of practical, physicochemical simulations of PEMFC device-scale performance and macroscopically observable behaviour. Reported models and their parameterisation (especially for Nafion 1100 materials) are compiled into a single source with consistent notation. Detailed attention is given to the Springer–Zawodzinski–Gottesfeld, Weber–Newman, and "binary friction model" methods of coupling proton transport with water uptake and diffusive water transport; alongside, data are compiled for the corresponding parameterisation of proton conductivity, water sorption isotherm, water diffusion coefficient, and electroosmotic drag coefficient. Subsequent sections address the formulation and parameterisation of models incorporating interfacial transport resistances, hydraulic transport of water, swelling and mechanical properties, transient and non-isothermal phenomena, and transport of dilute gases and other contaminants. Lastly, a section is dedicated to the formulation of models predicting the rate of membrane degradation and its influence on PEMFC behaviour. [ABSTRACT FROM AUTHOR]

Anion-conducting ionomer-based nanofibers mats are prepared by electrospinning (ES) technique. Depending on the relative humidity (RH) during the ES process (RHES), ionomer nanofibers with different morphologies are obtained. The effect of relative humidity on the ionomer nanofibers morphology, ionic conductivity, and water uptake (WU) is studied. A branching effect in the ES fibers found to occur mostly at RHES < 30% is discussed. The anion conductivity and WU of the ionomer electrospun mats prepared at the lowest RHES are found to be higher than in those prepared at higher RHES. This effect can be ascribed to the large diameter of the ionomer fibers, which have a higher WU. Understanding the effect of RH during the ES process on ionomer-based fibers' properties is critical for the preparation of electrospun fiber mats for specific applications, such as electrochemical devices. [ABSTRACT FROM AUTHOR]

A half-critical weight-average molecular weight ( M ¯ w ) (approximately 21,000 g mol−1), high-ion-content Zn-salt poly(styrene–ran–cinnamic-acid) (SCA–Zn) ionomer was successfully synthesized by styrene–cinnamic-acid (10.8 mol %) copolymerization followed by excess-ZnO melt neutralization. At 220 °C, the SCA–Zn's viscosity was only approximately 1.5 magnitude orders higher than that of commercial polystyrene (PS) at 102 s−1, and the PS/SCA–Zn (5–40 wt %) melt blends showed apparently fine, two-phased morphologies with blurred interfaces, of which the 95/5 and 90/10 demonstrated Han plots suggesting their near miscibility. These indicate that any PS–(SCA–Zn) processability mismatch was minimized by the SCA–Zn's half-critical M ¯ w despite its dense ionic cross-links. Meanwhile, the SCA–Zn's Vicat softening temperature (VST) was maximized by its cross-linking toward 153.1 °C, from that (97.7 °C) of PS, based on its half-critical M ¯ w at which the ultimate glass-transition temperature was approximated. Below approximately 110 °C, the PS/SCA–Zn (0–20 wt %) were seemingly miscible when their VST increased linearly yet slightly with the SCA–Zn fraction due to the dissolution of the SCA–Zn's cross-links. Nevertheless, the 60/40 blend's VST significantly diverged positively from the linearity until 111.1 °C, revealing its phase-separated morphology that effectively enhanced the heat resistance by the highly cross-linked SCA–Zn. This work proposes a methodology of improving PS heat resistance by melt blending with its half-critical M ¯ w , high-ion-content ionomer. [ABSTRACT FROM AUTHOR]

An MgO-templated mesoporous carbon, CNovel®, was employed as a catalyst support for the cathode of polymer electrolyte fuel cells (PEFCs) after modifying its dimensional, crystalline, surface and porous structures and the electrochemical oxygen reduction reaction (ORR) activities were examined by the thin-film rotating disk electrode (RDE) method and as well as the membrane electrode assembly (MEA) method. Although the catalytic activity of Pt on CNovel® was comparable with that on a non-porous carbon, Vulcan®, in the RDE configuration without Nafion®, Pt/CNovel showed a considerably higher activity than Pt/Vulcan in the MEA condition with Nafion®. The mechanism inducing this difference was discussed from the results of electrochemical surface area and sulfonic coverage measurements which suggested that Pt particles on inside pores of CNovel® are not covered with Nafion® ionomer while protons can still reach those Pt particles through water network. The MEA performance in the middle and high current-density regions was drastically improved by heat-treatment in air, which modified the pore structure to through-pored ones. [ABSTRACT FROM AUTHOR]