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At least 217 records · Page 12

Gas permeable fluoropolymers and ionomers

Novel copolymers that are fluoropolymers including a first repeat unit that is fluorinated and cyclic and a second repeat unit from a trifluorovinyl methylene ether monomer having sulfur or sulfone functionality in the pendant group are disclosed. The copolymers have relatively high gas permeability as a result of a cyclic repeat unit in the copolymer backbone and ionomers from oxidation of the sulfur containing functionality are particularity useful in the cathode structure of a proton exchange membrane fuel cell.

Lousenberg, Robert Daniel↗

Revealing the Crystalline Architecture of Semicrystalline Ion Exchange Membranes for the Design of Conductive and Durable Alkaline Anion Exchange Membranes

Alkaline anion exchange membrane (AAEM) fuel cells offer a cost-effective alternative to proton exchange membrane (PEM) fuel cells by eliminating the need for expensive precious metal catalysts. In both PEMs and AAEMs, semicrystalline polymers are a common choice, as the crystalline domains can act as mechanical reinforcements that limit swelling and promote mechanical durability in the material. However, spatially resolved characterization of crystalline organization in ion exchange membranes beyond ensemble-averaged X-ray scattering is underrepresented, likely in part due to ionization damage limitations in soft materials. Here, in this study, we resolve the nanometer-size crystallites in semicrystalline ion exchange membranes by applying cryogenic four-dimensional scanning transmission electron microscopy (cryo-4D-STEM) along with data-processing algorithms designed to optimize signals at a low dose to minimize radiation damage. We investigate the effects of synthesis components, including molecular weight and thermal treatment, on a model system of AAEMs in comparison to Nafion, the most commonly used and commercially successful PEM today. We find that excess water uptake in polymer membranes, a property directly associated with weak mechanical durability and with possible negative impacts on ion conductivity, can be reduced by over 30% by varying the polymer's crystalline morphology through changes in synthesis parameters such as molecular weight and thermal history. Our results indicate that this improvement is correlated with smaller crystalline domains with a more homogeneous distribution. More broadly, these results demonstrate how the crystalline architecture of polymer membranes can be tuned through their chemistry and thermal treatment in order to improve their conductivity and durability for commercial fuel cell performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-temperature low-humidity proton exchange membrane with “stream-reservoir” ionic channels for high-power-density fuel cells

The perfluorosulfonic acid (PFSA) proton exchange membrane (PEM) is the key component for hydrogen fuel cells (FCs). We used in situ synchrotron scattering to investigate the PEM morphology evolution and found a “stream-reservoir” morphology, which enables efficient proton transport. The short-side-chain (SSC) PFSA PEM is fabricated under the guidance of morphology optimization, which delivered a proton conductivity of 193 milliSiemens per centimeter [95% relativity humidity (RH)] and 40 milliSiemens per centimeter (40% RH) at 80°C. The improved glass transition temperature, water permeability, and mechanical strength enable high-temperature low-humidity FC applications. Performance improvement by 82.3% at 110°C and 25% RH is obtained for SSC-PFSA PEM FCs compared to Nafion polymer PEM devices. The insights in chain conformation, packing mechanism, crystallization, and phase separation of PFSAs build up the structure-property relationship. In addition, SSC-PFSA PEM is ideal for high-temperature low-humidity FCs that are needed urgently for high-power-density and heavy-duty applications.

25 ENERGY STORAGE↗

A New Simultaneous Membrane Thickness and Catalyst Loading Measurement for Fuel Cell Proton-Exchange Assemblies by $\mathrm{IR}$ Transmission

Here, we present a study of mid-infrared (mid-IR) transmission through typical proton-exchange fuel cell and water electrolyzer catalyst-coated membrane materials, and the determination of membrane layer thickness, and catalyst layer loading, from the power of the transmitted beam. Measured membrane thicknesses lay in the range of 25-125 um, and catalyst areal loadings range from 0.05 to 0.35 mg/cm 2 . We show that the transmission spectrum correlated to membrane thickness and catalyst loading values separately, and also used a mathematical model to calculate both quantities simultaneously, from a single measurement of transmission. Measurements were carried out using a Fourier-transform infrared (FTIR) spectrometer, in specular transmission mode, in the wavelength range of 3-13 um (3333-770 cm -1 ). We discuss the potential application of this method to the development of roll-to-roll manufacturing full-area-scanning quality inspection of catalyst-coated membrane (CCM) materials.

30 DIRECT ENERGY CONVERSION↗

Membrane Degradation in PEM Fuel Cells: Part I. Modeling Gas Crossover and the Pt Band

Understanding chemical degradation of the proton-exchange membrane in fuel cells is crucial for extending their lifetimes. Herein, various degradation reactions reported in literature are organized and analyzed, including direct radical generation and an indirect (Fenton) pathway. To understand the transport of dissolved H 2 and O 2 crossover gases as they relate to membrane degradation, an agglomerate-scale model is introduced, treating gas, ionomer, and catalyst as discrete phases. The model reveals a key phenomenon: at working potentials, dissolved gases are mostly consumed at the interface between the catalyst layer and the membrane, leaving little gas to cross the membrane. Under open-circuit conditions, dissolved gases are not consumed and can then cross the membrane. This explains high H 2 O 2 concentrations and degradation rates seen in experiments but not captured in previous models. Following mixed-potential theory, crossover gases supply the hydrogen-oxidation and oxygen-reduction reactions, which occur simultaneously on individual Pt particles comprising the Pt band in the membrane, forming reactive species (H 2 O 2 , OH·). Results show crossover gas almost entirely reacts on the Pt band, allowing little to reach the opposite electrode. Furthermore, the micro-scale geometry of the catalyst-layer/membrane interface impacts the gas crossover at working potentials, indicating that cell construction affects membrane durability.

Johnson, Evan F. [Lawrence Berkeley National Labor↗

Polymer Electrolytes with High Ionic Concentration for Fuel Cells and Electrolyzers

As fuel cells and electrolyzers require higher performance and durability, the design aspects of polymer electrolytes continue to evolve. One distinctive trend in achieving a remarkably improved performance of electrochemical devices is to equip polymer electrolytes with high ionic concentration. This Review presents recent implementations of polymer electrolytes with a high ionic concentration in electrochemical devices. The synthetic approaches, benefits in device performance, challenges, and prospects of polymer electrolytes are summarized. The goal of this article is to explain the working principles of polymer electrolytes with a high acid concentration in high-performing fuel cells and electrolyzers, to survey recent achievements, and to address remaining technical issues. As well as informing polymer scientists, this Review may generate interest in the broader community of emerging fields to make use of these promising materials in tackling tough scientific challenges.

30 DIRECT ENERGY CONVERSION↗

Review—Meeting Fuel Cell Catalyst Requirements for Heavy-Duty Vehicle Applications

Catalyst requirements for proton exchange membrane (PEM) fuel cells differ by applications. Commercial heavy-duty vehicle (HDV) applications consume more H 2 fuel and demand higher durability than many others and the total cost of ownership (TCO) of the vehicle is largely related to the performance and durability of catalysts. This article is written to bridge the gap between the industrial requirements and academic activity for advanced cathode catalysts with an emphasis on durability. From a materials perspective, the underlying nature of the carbon support, Pt-alloy crystal structure, stability of the alloying element, cathode ionomer volume fraction, and catalyst-ionomer interface play a critical role in improving performance and durability. We provide our perspective on four major approaches, namely, mesoporous carbon supports, ordered PtCo intermetallic alloys, thrifting ionomer volume fraction, and shell-protection strategies that are currently being pursued. While each approach has its merits and demerits, their key developmental needs for future are highlighted.

Ramaswamy, Nagappan (ORCID:0000000234302758)↗

Critical Parameter Identification of Fuel-Cell Models Using Sensitivity Analysis

Numerical modeling has been a vital tool in proton-exchange-membrane fuel-cell (PEMFC) analysis; however, the predictive capabilities of these models depend on the input physical parameters, several of which are either not experimentally measured or have large scatter in measured values. This article presents an uncertainty propagation-based sensitivity analysis to identify the model parameters that impact the model predictions most. A comprehensive 2-D membrane electrode assembly (MEA) model is used to perform local sensitivity analysis at multiple operating conditions, which encompass the range of environments and operating conditions a cell can encounter. While at lower humidities, cathode kinetics and membrane-ohmic-loss related parameters are crucial, gas transport and porous-media saturation behavior are more important at humidified conditions. Several of these findings are different from previous studies presented in literature. Identifying the crucial parameters helps focus future material and cell optimization studies as well as experimental studies to quantify these parameters with higher accuracy.

25 ENERGY STORAGE↗

Degradation of Fuel Cell Membrane Electrode Assemblies from Buses Operated More than 25,000 h

This study investigates the performance losses and degradation of proton-exchange-membrane fuel-cell stacks taken from the Alameda Contra Costa Transit District (AC Transit) bus system (Alameda and Contra Costa counties, California, United States) that were operated for over 25,000 h. Here, we focus on the origin of differences in electrochemical performance between beginning-of-life (BOL) and end-of-life states as well as diagnostic data acquired during the lifetime of the buses. In doing so, we employ in- and ex- situ characterization methods such as polarization curves, electrochemical impedance spectroscopy, electron microscopy, and X-ray characterization. Uniform degradation of the catalyst layer including Pt agglomeration/migration and electrode thinning was observed in all of the post-teardown measurements compared to BOL materials resulting from years of field operation. Despite these changes, the measured post-teardown performance suggests a sufficient output for the expected load, which indicate factors other than degradation of the membrane-electrode assemblies (MEAs) are likely responsible for the decommissioning of the stacks. The findings indicate that these MEA materials can enable long lifetime in fuel-cell vehicles, if the MEAs are not subjected to adverse operating conditions. The results also highlight the need for more in-vehicle diagnostics to maximize the lifetime of fuel cell vehicle (FCV) powerplants.

25 ENERGY STORAGE↗

Effect of Carbon Support Heat Treatment on the Performance of Ion-Pair High-Temperature PEM Fuel Cells

Heat treatment can significantly alter the physical and chemical properties of carbon supports, thereby influencing the performance of proton exchange membrane (PEM) fuel cells. This study explores how varying carbon heat treatment temperatures—from 1,000 °C to 2,200 °C—affect the structure and performance of platinum-based catalysts in high-temperature PEM fuel cells. Increasing the heat treatment temperature led to a notable decrease in surface area, along with increases in carbon grain size and hydrophobicity. Although the catalyst supported on carbon treated at 1,000 °C exhibited the highest catalyst activity, the MEA using carbon treated at 1,500 °C delivered the best overall fuel cell performance. This is attributed to an optimized balance between hydrophobicity and accessible surface area, which enhances water management and catalyst utilization. These findings underscore the importance of carbon support engineering in improving the efficiency of ion-pair high-temperature PEM fuel cells.

08 HYDROGEN↗

Computer Simulation of Proton Transport in Fuel Cell Membranes (Final Report)

This DOE-supported research grant focused on understanding the nature of proton transport in complex systems such as proton exchange membranes (PEMs). The most unique aspect of the research was the development and implementation of a novel multiscale reactive molecular dynamics (MS-RMD) methodology. In this approach, covalent bonds can dynamically break and form, allowing one to accurately treat the proton hopping process essential to capturing the physics of proton transport. The Voth group applied this method to proton exchange membrane systems, providing insight into their proton transport mechanism. They found that protons can diffuse most rapidly in the water-rich regions, but that protons actually spend so little time in such regions that transport along the hydrophobic – hydrophilic interface controls the membrane performance. In addition, the group worked to increase understanding of acidic solutions, developing methods for simulating and interpreting experimental infrared vibrational spectroscopy for excess protons (acidic solutions). The group also implemented novel tools for developing proton transport reactive MD models using a relative entropy minimization scheme.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of Catalyst Ink Dispersing Solvent on PEM Fuel Cell Performance and Durability

The dispersing solvent used for fuel cell catalyst ink preparation plays a vital role in establishing the resulting morphology of the electrode layers, which in turn will impact the performance of proton exchange membrane (PEM) fuel cells. In this study, we report the impact of various ionomer dispersion solvents on PEM fuel cell performance and durability; two aqueous (1-propanol/water and 2-propanol/water) and several non-aqueous dispersing solvents (ethylene glycol and 1,2-butanediol) are compared. The cathode catalyst layer (CCL) fabricated using inks prepared with 1-propanol/water (3:1, w/w) exhibited the best initial performance followed by the CCL prepared using ethylene glycol. The CCLs made from non-aqueous ethylene glycol and 1,2-butanediol exhibited the best durability upon accelerated stress testing. Scanning transmission electron microscopy combined with energy dispersive X-ray spectroscopy indicated that, after the stress test, the distribution of both the Nafion ionomer and Pt nanoparticles within the CCLs prepared with non-aqueous ionomer dispersions underwent less change than those prepared with aqueous dispersions, which is responsible for the improved durability

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗