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Weber, Adam Z.

Publications and source records attributed to Weber, Adam Z..

At least 163 records · Page 9

Nanostructure/Swelling Relationships of Bulk and Thin-Film PFSA Ionomers

Perfluorinated sulfonic acid (PFSA) ionomers are the most widely used solid electrolyte in electrochemical technologies due to their remarkable ionic conductivity with simultanous mechanical stability, imparted by their phase-separated morphology. In this work, the morphology and swelling of PFSA ionomers (Nafion and 3M) as bulk membranes (>10 μm) and dispersion-cast thin films (<100 nm) are investigated to identify the roles of equivalent weight (EW) and side-chain length across lengthscales. Humidity-dependent structural changes as well as different PFSA chemistries are explored in the thin-film regime, allowing for the development of thickness-EW phase diagrams. The ratio of macroscopic (thickness) to nanoscopic (domain spacing) swelling during hydration is found to be affine (1:1) in thin films, but increases as the thickness approaches bulk values, revealing the existence of a mesoscale organization governing the multiscale swelling in PFSAs. Ionomer chemistry, in particular EW, is found to play a key role in altering the confinement-driven structural changes, including thin-film anisotropy, with phase separation becoming weaker as the film thickness is reduced below 25 nm or as EW is increased. Lastly, for the lower-EW 3M PFSA ionomers, confinement appears to induce even stronger phase separation accompanied by domain alignment parallel to the substrate.

36 MATERIALS SCIENCE↗

A Review of Hydrogen/Halogen Flow Cells

Flow batteries provide an energy-storage solution for various grid-related stability and service issues that arise as renewable-energy-generation technologies are adopted. Among the most promising flow-battery systems are those using hydrogen/halogen redox couples, which promise the possibility of meeting the cost target of the US Department of Energy (DOE), due to their fast and reversible kinetics and low materials cost. However, significant critical issues and barriers for their adoption remain. In this review of halogen/hydrogen systems, technical and performance issues, and research and development progress are reviewed. The information in this review can be used as a technical guide for research and development of related redox-flow-battery systems and other electrochemical technologies.

25 ENERGY STORAGE↗

Understanding Impacts of Catalyst-Layer Thickness on Fuel-Cell Performance via Mathematical Modeling

In this article, a two-dimensional, multiphase, transient model is introduced and used to explore the impact of catalyst-layer thickness on performance. In particular, the tradeoffs between water production and removal through transport or evaporation are highlighted, with a focus on low-temperature performance. For the latter, a case study of an ultra-thin catalyst layer is undergone to explore how various material properties alter the steady-state and startup performance of a cell. The findings provide understanding and guidance to optimize fuel-cell performance with thin electrodes.

25 ENERGY STORAGE↗

A Computational Study of Optically Concentrating, Solar-Fuels Generators from Annual Thermal- and Fuel-Production Efficiency Perspectives

The commercial deployment of wireless photoelectrochemical cells (PECs) may provide a viable means to close the anthropogenic carbon cycle associated with the global transportation sector. The growing body of research on PECs has largely focused on developing and integrating the materials necessary for robust, efficient solar-fuel production on the laboratory benchtop. While these efforts are a prerequisite for the commercialization of PECs, deployed PECs will have to contend with extreme heat, cold, and insolation variations in the outdoor environment. They will also have to operate efficiently throughout their lifetime and in multiple locations. This paper reports a computational framework for estimating the hourly profiles of time-varying temperature and solar-to-hydrogen efficiency that optically concentrating, wireless PECs will attain over the course of a typical year. It is found that annual weighted average solar-to-hydrogen efficiencies in excess of 9 to 11% can be achieved in extremely cloudy and sunny locations, respectively. Additionally, typical PECs will likely incur damage due to overheating or freezing; measures to protect PECs from extreme heat and cold are outlined. Here, the findings also help to bring into focus issues regarding real-world deployment of energy-generation technologies and methodologies towards tackling them.

25 ENERGY STORAGE↗

Stable Aqueous Dispersions of Hydrophobically Modified Titanium Dioxide Pigments through Polyanion Adsorption: Synthesis, Characterization, and Application in Coatings

Polyanion dispersants stabilize aqueous dispersions of hydrophilic (native) inorganic oxide particles, including pigments currently used in paints, which are used at an annual scale of 3 million metric tons. While obtaining stable aqueous dispersions of hydrophobically modified particles has been desired for the promise of improved film performance and water barrier properties, it has until now required either prohibitively complex polyanions, which represent a departure from conventional dispersants, or multistep syntheses based on hybrid-material constructs. Here, we demonstrate the aqueous dispersion of alkylsilane-capped inorganic oxide pigments with conventional polycarboxylate dispersants, such as carboxymethylcellulose (CMC) and polyacrylate, as well as a commercial anionic copolymer. Contact-angle measurements demonstrate that the hydrophobically modified pigments retain significant hydrophobic character even after adsorbing polyanion dispersants. CMC adsorption isotherms demonstrate 92% greater polyanion loading on trimethylsilyl modified hydrophobic particles relative to native oxide at pH 8. However, consistent with prior literature, hydrophobically modified silica particles adsorb polyanions very weakly under these conditions. These data suggest that Lewis acidic heteroatoms such as Al 3+ sites on the pigment surface are necessary for polyanion adsorption. The adsorbed polyanions increase the dispersion stability and zeta potential of the particles. Based on particle sedimentation under centrifugal force, the hydrophobically modified pigments possess greater dispersion stability with polyanions than the corresponding native hydroxylated particles. The polyanions also assist in the aqueous wetting of the hydrophobic particles, facilitating the transition from a dry powder into an aqueous dispersion of primary particles using less agitation than the native hydroxylated pigment. The application of aqueous dispersions of hydrophobically modified oxide particles to waterborne coatings leads to films that display lower water uptake at high relative humidities and greater hydrophilic stain resistances. Finally, this improved film performance with hydrophobically modified pigments is the result of better association between latex polymer and pigment in the dry film.

36 MATERIALS SCIENCE↗

All-Iron Redox Flow Battery Tailored for Off-Grid Portable Applications

We proposed and developed an all-iron redox flow battery for end users without access to an electricity grid. The concept is a low-cost battery which the user assembles, discharges, and then disposes of the active materials. Our design goals are: (1) minimize upfront cost, (2) maximize discharge energy, and (3) utilize non-toxic and environmentally benign materials. These are different goals than typically considered for electrochemical battery technology, which provides the opportunity for a novel solution. The selected materials are: low-carbon-steel negative electrode, paper separator, porous-carbon-paper positive electrode, and electrolyte solution containing 0.5 m Fe 2 (SO 4 ) 3 active material and 1.2 m NaCl supporting electrolyte. Furthermore, with these materials, an average power density around 20 mW cm -2 and a maximum energy density of 11.5 Wh L -1 are achieved. A simple cost model indicates the consumable materials cost US$6.45 per kWh -1 , or only US$0.034 per mobile phone charge.

25 ENERGY STORAGE↗

Electrochemical/Mechanical Coupling in Ion-Conducting Soft Matter

Mechanical and electrochemical phenomena exhibit many interesting multidirectional couplings in ion-exchange soft matter due to their intrinsic material physiochemical states and responses to environmental stressors. Such coupling is explored in terms of recent studies with a focus on the degradation of polymer-electrolyte fuel-cell membranes. In addition, (electro)chemical–mechanical coupling of ion-conducting polymers in other applications is also introduced, as there is a research need to explore the interactions between these often wrongly assumed disparate fields in order to optimize, exploit, and discover new technologies and applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of hygrothermal aging on structure/function relationship of perfluorosulfonic-acid membrane

Perfluorosulfonic-acid (PFSA) membranes are widely used as the solid electrolyte in electrochemical devices where their main functionalities are ion (proton) conduction and gas separation in a thermomechanically stable matrix. Due to prolonged operational requirements in these devices, PFSA membranes’ properties change with time due to hygrothermal aging. This paper studies the evolution of PFSA structure/property relationship changes during hygrothermal aging, including chemical changes leading to changes in ion-exchange capacity (IEC), nanostructure, water-uptake behavior, conductivity, and mechanical properties. Our findings demonstrate that with hygrothermal aging, the storage modulus increases, while IEC and water content decrease, consistent with the changes in nanostructure, that is, water- and crystalline-domain spacings inferred from small- and wide-angle X-ray scattering (SAXS/WAXS) experiments. In addition, the impact of aging is found to depend on the membrane's thermal prehistory and post-treatments, although universal correlations exist between nanostructural changes and water uptake. Lastly, the findings have impact on understanding lifetime, durability, and use of these and related polymers in various technologies.

30 DIRECT ENERGY CONVERSION↗

Durability Improvements Through Degradation Mechanism Studies

The durability of polymer electrolyte membrane (PEM) fuel cells is a major barrier to the commercialization of these systems for stationary and transportation power applications. By investigating cell component degradation modes and defining the fundamental degradation mechanisms of components and component interactions, new materials can be designed to improve durability. To achieve a deeper understanding of PEM fuel cell durability and component degradation mechanisms, we utilize a multi-institutional and multi-disciplinary team with significant experience investigating these phenomena.

08 HYDROGEN↗

Impact of membrane characteristics on the performance and cycling of the Br-2-H-2 redox flow cell

The Br-2/H-2 redox flow cell shows promise as a high-power, low-cost energy storage device. In this paper, the effect of various aspects of material selection and processing of proton exchange membranes on the operation of the Br-2/H-2 redox flow cell is determined. Membrane properties have a significant impact on the performance and efficiency of the system. In particular, there is a tradeoff between conductivity and crossover, where conductivity limits system efficiency at high current density and crossover limits efficiency at low current density. The impact of thickness, pretreatment procedure, swelling state during cell assembly, equivalent weight, membrane reinforcement, and addition of a microporous separator layer on this tradeoff is assessed. NR212 (50 mu m) pretreated by soaking in 70 degrees C water is found to be optimal for the studied operating conditions. For this case, an energy efficiency of greater than 75% is achieved for current density up to 400 mA cm(-2), with a maximum obtainable energy efficiency of 88%. A cell with this membrane was cycled continuously for 3164 h. Membrane transport properties, including conductivity and bromine and water crossover, were found to decrease moderately upon cycling but remained higher than those for the as-received membrane. (C) 2015 Elsevier B.V. All rights reserved.

Tucker, MC↗

Interactions between liquid-water and gas-diffusion layers in polymer-electrolyte fuel cells

Over the past few decades, a significant amount of research on polymer-electrolyte fuel cells (PEFCs) has been conducted to improve performance and durability while reducing the cost of fuel cell systems. However, the cost associated with the platinum (Pt) catalyst remains a barrier to their commercialization and PEFC durability standards have yet to be established. An effective path toward reducing PEFC cost is making the catalyst layers (CLs) thinner thus reducing expensive Pt content. The limit of thin CLs is high gas-transport resistance and the performance of these CLs is sensitive to the operating temperature due to their inherent low water uptake capacity, which results in higher sensitivity to liquid-water flooding and reduced durability. Therefore, reducing PEFC's cost by decreasing Pt content and improving PEFC's performance and durability by managing liquid-water are still challenging and open topics of research. An overlooked aspect nowadays of PEFC water management is the gas-diffusion layer (GDL). While it is known that GDL's properties can impact performance, typically it is not seen as a critical component. In this work, we present data showing the importance of GDLs in terms of water removal and management while also exploring the interactions between liquid-water and GDL surfaces. The critical interface of GDL and gas-flow-channel in the presence of liquid-water was examined through systematic studies of adhesion forces as a function of water-injection rate for various GDLs of varying thickness. GDL properties (breakthrough pressure and adhesion force) were measured experimentally under a host of test conditions. Specifically, the effects of GDL hydrophobic (PTFE) content, thickness, and water-injection rate were examined to identify trends that may be beneficial to the design of liquid-water management strategies and next-generation GDL materials for PEFCs.

30 DIRECT ENERGY CONVERSION↗

Probing water distribution in compressed fuel-cell gas-diffusion layers using X-ray computed tomography

X-ray computed tomography was used to investigate geometrical land and channel effects on spatial liquid-water distribution in gas-diffusion layers (GDLs) of polymer-electrolyte fuel cells under different levels of compression. At low compression, a uniform liquid-water front was observed due to water redistribution and uniform porosity; however, at high compression, the water predominantly advanced at locations under the channel for higher liquid pressures. Lastly, at low compression, no apparent correlation between the spatial liquid water and porosity distributions was observed, whereas at high compression, a strong correlation was shown, indicating a potential for smart GDL architecture design with modulated porosity.

25 ENERGY STORAGE↗

Resistor-Network Modeling of Ionic Conduction in Polymer Electrolytes

A resistor- and pore-network methodology is used here to examine transport of ions in various ion-conducting polymers. The model is used to examine ion conduction in random and correlated (at the mesoscale) distributions of high and low conductive domains showing the impact that defects or different conduction modes have on overall effective conductivity and percolation. The specific case of Nafion is modeled where swelling is accounted for as well as a spatially varying conductivity within the nanodomains. The model is also used to investigate conduction in thin-films, where a substantial drop in conductivity is witnessed for films less than 50 nm thick. The model shows good agreement with experimental data and provides a methodology for efficient multiscale modeling of transport in ion-conducting polymers from the nanoscale morphology through the mesoscale transport pathways to the observable macroscale properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗