122 research outputs found

    Morphology of Anion-Conducting Ionenes Investigated by X-ray Scattering and Simulation

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    We have studied the morphology of a novel series of benzimidazole-based ionenes, methylated poly(hexamethyl-p-terphenylbenzimidazolium) (HMT-PMBI), in halide form. Materials with anion-exchange capacities ranging from 0 to 2.5 mequiv/g were studied. X-ray scattering reveals three length scales in the materials: ion–polymer spacing (4 Å), polymer–polymer interchain spacing (6 Å), and an intrachain repeat distance (20 Å). No long-range structure is apparent above the monomer length, which is rare in ion-conducting polymer membranes. In preliminary molecular dynamics simulations, water molecules were observed forming chains between ions, even at a modest level of hydration, providing an interpenetrating network where conductivity can occur

    Progression in the Morphology of Fuel Cell Membranes upon Conjoint Chemical and Mechanical Degradation

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    Ionomer membranes used to separate the electrodes in polymer electrolyte fuel cells are known to degrade both chemically and mechanically during regular fuel cell operation and may ultimately result in lifetime-limiting failure. The objective of the present work is to understand the effects of combined chemical and mechanical stresses on the mesoscale morphology of the membrane and its role in the overall degradation process. The mesoscale effects of sulfonic acid group loss and fluoride release on the phase segregated morphology of the membrane are analyzed using contrast-enhanced transmission electron microscopy and energy dispersive X-ray spectroscopy. The end-of-life ionic domain size of the ionomer is shown to be substantially enlarged compared to the pristine membrane state. Elemental mapping overlayed with the binary ionic and non-ionic morphology reveals mesoscopic void regions in the degraded material that are depleted of ionomer fluorine and carbon and considered susceptible to micro-crack initiation. A larger, severely degraded void region is also identified which contains evidence of hygrothermal stress induced localized ionomer crazing as a potential nucleation site for macroscopic fracture development. The synergetic effects of chemical and mechanical degradation on the progressive changes in the observed mesoscale morphology are discussed

    Towards a stable ion-solvating polymer electrolyte for advanced alkaline water electrolysis

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    Steric hindrance is employed as a design strategy of polybenzimidazoles for ion-solvating polymer electrolyte membrane alkaline water electrolysis.</p

    Characterization of pore network structure in catalyst layers of polymer electrolyte fuel cells

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    We model and validate the effect of ionomer content and Pt nanoparticles on nanoporous structure of catalyst layers in polymer electrolyte fuel cells. By employing Pore network modeling technique and analytical solutions, we analyze and reproduce experimental N2-adsorption isotherms of carbon, Pt/ carbon and catalyst layers with various ionomer contents. The porous catalyst layer structures comprise of Ketjen Black carbon, Pt and Nafion ionomer. The experimental pore size distributions obtained by N2- adsorption are used as an input to generate porous media using the pore network approach. Subsequently, the simulated porous structures are used to produce simulated N2-adsorption isotherms, which are then compared to the experimentally measured isotherms. The results show a good agreement in the prediction of the effect of the ionomer content on the microstructure of catalyst layers. Moreover, the analysis of the isotherms confirms the hypothesis of ionomer distribution on the surface of agglomerates as well as the existence of different sorption regimes in primary and secondary pores of fuel cell catalyst layers

    Leaping and Landing in Brave Spaces

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    Vapor-fed electrolysis of water has been performed using membrane-electrode assemblies (MEAs) incorporating earth-abundant catalysts and bipolar membranes (BPMs). Catalyst films containing CoP nanoparticles, carbon black, and Nafion were synthesized, characterized, and integrated into cathodes of MEAs. The CoP-containing MEAs exhibited stable (>16 h) vapor-fed electrolysis of water at room temperature at a current density of 10 mA cm⁻² with 350 mV of additional overvoltage relative to MEA's formed from Pt/C cathodic electrocatalysts due to slower hydrogen-evolution reaction kinetics under vapor-fed conditions and fewer available triple-phase boundaries in the catalyst film. Additionally, catalyst films containing a [NiFe]-layered double hydroxide ([NiFe]-LDH) as well as a hydroxide ion conductor, hexamethyl-p-terphenyl poly(benzimidazolium) (HMT-PMBI), were synthesized, characterized, and integrated into the anodes of the MEAs. The [NiFe]-LDH-containing MEAs exhibited overvoltages at 10 mA cm⁻² that were similar to those of IrO_x-containing MEAs for vapor-fed electrolysis of water at room temperature. A BPM was formed by pairing Nafion with HMT-PMBI, resulting in a locally alkaline environment of HMT-PMBI to stabilize the [NiFe]-LDH and a locally acidic environment to stabilize the CoP. BPM-based MEAs were stable (>16 h) for vapor-fed electrolysis of water at room temperature at a current density of 10 mA cm⁻², with a change in the pH gradient of 1 unit over 16 h of electrolysis for IrOx-containing MEAs. The stability of [NiFe]-LDH-based MEAs under vapor-fed conditions was dependent on the catalyst film morphology and resulting BPM interface, with stable operation at 10 mA cm⁻² achieved for 16 h. All MEAs exhibited a drift in the operating voltage over time associated with dehydration. These results demonstrate that earth-abundant catalysts and BPMs can be incorporated into stable, room-temperature, vapor-fed water-splitting cells operated at 10 mA cm⁻²

    Poly(Bis-Arylimidazoliums) Possessing High Hydroxide Ion Exchange Capacity and High Alkaline Stability

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    Solid polymer electrolyte electrochemical energy conversion devices that operate under highly alkaline conditions afford faster reaction kinetics and the deployment of inexpensive electrocatalysts compared with their acidic counterparts. The hydroxide anion exchange polymer is a key component of any solid polymer electrolyte device that operates under alkaline conditions. However, durable hydroxide-conducting polymer electrolytes in highly caustic media have proved elusive, because polymers bearing cations are inherently unstable under highly caustic conditions. Here we report a systematic investigation of novel arylimidazolium and bis-arylimidazolium compounds that lead to the rationale design of robust, sterically protected poly(arylimidazolium) hydroxide anion exchange polymers that possess a combination of high ion-exchange capacity and exceptional stability

    Star polymers of sodium styrenesulfonate prepared by one-pot TEMPO-controlled SFRP

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    Star polymers of sodium styrenesulfonate with controlled arm length were prepared in a one-pot polymerization. Sodium styrenesulfonate was first polymerized with controlled molecular weight and narrow polydispersity by stable free radical polymerization. Poly(sodium styrenesulfonate) was terminated with divinyl benzene and star polymers prepared via stable free radical coupling of vinylic terminal groups. Star polymers based on arms of 20 and 32 repeat units possessed ~33 and ~41 arms per star respectively. Formation of star polymers with much longer arms was limited by poor coupling kinetics.Peer reviewed: YesNRC publication: N
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