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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Atomic layer deposition for surface area determination of solid oxide electrodes

Surface area measurements are important for characterizing porous solids, but commonly used methods such as Brunauer–Emmett–Teller (BET) gas adsorption and computed nanotomography are lacking for certain applications such as the development of solid oxide fuel cell electrodes, which often have absolute surface areas <1 m 2 and contain nanoscale features. Presented is a novel method for the surface area determination of samples with total measurable areas of 1–1000 cm 2 with a standard deviation ± 1 cm 2 , utilizing the atomic layer deposition (ALD) of Al 2 O 3 over microstructurally complex internal porosity. The volume of alumina is then quantified using plasma spectroscopy and converted to an area using the known ALD layer thickness. Under the modest ALD reactor soak times used (8.5 s), the precursor penetration depth is found to be ~50 μm, exceeding the requirement for uniformly coating SOFC functional layers. A model system, (La 0.8 Sr 0.2 ) 0.98 MnO 3–δ /Ce 0.9 Gd 0.1 O 1.95 (LSM/GDC) scaffolds of ~2.7 m 2 g –1 , was measured using the technique and compared against the BET method, and comparable results were obtained but with 1000 times less material needed. The technique is demonstrated for measurements in two example areas of active SOFC research: exsolved (Ni, Fe) nanoparticles on an Sr(Ti, Fe, Ni)O 3–δ electrode and PrO x catalyst nanoparticles infiltrated onto LSM/GDC scaffolds. Finally, the technique may be broadly useful wherever the accurate surface area determination of small absolute quantities of porous ceramic structures on the order of 0.1–50 m 2 g –1 is sought.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Application of Molecular Catalysts for the Oxygen Reduction Reaction in Alkaline Fuel Cells

Here, the development of precious group metal-free (PGM-free) catalysts for the oxygen reduction reaction is considered as the main thrust for the cost reduction of fuel cell technologies and their mass production. Within the PGM-free category, molecular catalysts offer an advantage over other heat-treated PGM-free catalysts owing to their well-defined structure, which enables further design of more active, selective, and durable catalysts. Even though non-heat-treated molecular catalysts with exceptional performance have been reported in the past, they were rarely tested in a fuel cell. Herein, we report on a molecular catalyst under alkaline conditions: fluorinated iron phthalocyanine (FeFPc) supported on cheap and commercially available high-surface area carbon-BP2000 (FeFPc@BP2000). It exhibits the highest activity ever reported for molecular catalysts under alkaline conditions in half-cells and fuel cells.

25 ENERGY STORAGE↗
DOE OSTI2023

Surface Oxygen Depletion of Layered Transition Metal Oxides in Li-Ion Batteries Studied by Operando Ambient Pressure X-ray Photoelectron Spectroscopy

A new operando spectro-electrochemical setup was developed to study oxygen depletion from the surface of layered transition metal oxide particles at high degrees of delithiation. An NCM111 working electrode was paired with a chemically delithiated LiFePO 4 counter electrode in a fuel cell-inspired membrane electrode assembly (MEA). A propylene carbonate-soaked Li-ion conducting ionomer served as an electrolyte, providing both good electrochemical performance and direct probing of the NCM111 particles during cycling by ambient pressure X-ray photoelectron spectroscopy. The irreversible emergence of an oxygen-depleted phase in the O 1s spectra of the layered oxide particles was observed upon the first delithiation to high state-of-charge, which is in excellent agreement with oxygen release analysis via mass spectrometry analysis of such MEAs. By comparing the metal oxide-based O 1s spectral features to the Ni 2p 3/2 intensity, we can calculate the transition metal-to-oxygen ratio of the metal oxide close to the particle surface, which shows good agreement with the formation of a spinel-like stoichiometry as an oxygen-depleted phase. This new setup enables a deeper understanding of interfacial changes of layered oxide-based cathode active materials for Li-ion batteries upon cycling.

25 ENERGY STORAGE↗
DOE OSTI2024

Advanced Anion Exchange Membranes with Tunable Water Transport for PGM-Free AEMFCs

This project advanced the synthesis, characterization, and testing of anion exchange membranes for use in fuel cells. Our goal was to improve the water transport in anion exchange membrane fuel cells to improve their performance and durability. Through the work in this project we: 1) developed new composite anion exchange membranes through polymer synthesis and membrane casting into mechanical supports; 2) optimized electrode architecture and cell conditions to achieve; 3) demonstrated an integrated approach to achieving over 1 W/cm 2 in an operating device. While we did not achieve 1000 hours of continuous operation, we demonstrated multiple runs of more than 300 hours of device performance at steady-state.

08 HYDROGEN↗
DOE OSTI2020

Patterned electrode catalyst

Disclosed herein are embodiments of a patterned electrode comprising regions of catalyst and segregating regions that separate the regions of catalyst. The segregating regions may be regions of non-catalytic material. The catalyst regions may correspond to the channels of a flow field. The electrode provides improved fuel cell performance, particularly at high current densities. The electrode may be for all suitable applications, such as in a membrane electrode assembly and/or a fuel cell. Also disclosed is a method for making the patterned electrode. The method may comprise using masks to apply the catalyst and non-catalyst material to a substrate.

Macauley, Natalia↗
DOE OSTI2020

Utilizing ink composition to tune bulk-electrode gas transport, performance, and operational robustness for a Fe-N-C catalyst in polymer electrolyte fuel cell

With lower site density and turnover frequency, platinum group metal (PGM)-free catalysts based electrodes are often greater than 50 mu m thick in order to increase performance across the fuel cell operating range. Consequently, PGM-free electrodes have an additional bulk electrode transport resistance beyond the local or aggregate level transport in thin platinum-based electrodes. In parallel to the development of more active and durable PGM-free catalysts, advancements in understanding the interplay between PGM-free electrode fabrication, bulk-electrode transport, proton conductivity and performance are needed. Here, the relationship between ionic and gas phase transport through the electrode thickness is modified by adjusting electrocatalyst and ionomer flocculation/interaction at the ink level. The influence of the ink composition (water/n-propanol content) is examined via various in-situ electrochemical and ex-situ characterization techniques and the resulting electrode structure/performance relationship contrasted with electrode performance robustness across a range of relative humidity (RH). For the electrocatalyst examined here, a water-rich (82 wt% H2O) ink formulation was favorable for operation at high RH due to improved molecular diffusion through larger electrode pores. In contrast, the improved interactions between ionomer and electrocatalyst enabled a more robust electrode and higher performance during low RH operation for the 50 wt% H2O content ink.

08 HYDROGEN↗
DOE OSTI2026

BIL High Speed Fuel Cell Stack Manufacturing

General Motors LLC (GM) was awarded a project to develop and implement technologies for manufacturing 20,000 units of Fuel Cell Stacks per year on two shifts per day basis. GM leveraged prior in-house expertise in designing the Fuel Cells, deploying the manufacturing process steps in the laboratory environment as well as the deployment in the industrial environment on a smaller scale. The project focus was to design, build, and deploy a manufacturing line consisting of an anode and cathode electrode processing, unitized electrode assembly, fuel cell stacking, compression, testing, and final assembly of the fuel cell stack. The project was terminated in the first budget period.

08 HYDROGEN↗
NASA NTRS2004

Electrode and interconnect for miniature fuel cells using direct methanol feed

An improved system for interconnects in a fuel cell. In one embodiment, the membranes are located in parallel with one another, and current flow between them is facilitated by interconnects. In another embodiment, all of the current flow is through the interconnects which are located on the membranes. The interconnects are located between two electrodes.

Narayanan, Sekharipuram R.↗
DOE OSTI2023

Physics-Based Model to Represent Membrane-Electrode Assemblies of Solid-Oxide Fuel Cells Based on Gadolinium-Doped Ceria

This paper reports a physics-based model that predicts membrane-electrode assembly (MEA) performance of solid-oxide fuel cells (SOFCs) with Ce 0.9 Gd 0.1 O 2− δ (GDC10) electrolyte membranes. The paper derives self-consistent thermodynamic and transport properties for GDC1o mobile charged defects (oxide vacancies and reduced-ceria small polarons) by fitting published measurements of oxygen non-stoichiometry and conductivity over ranges of temperature and O 2 partial pressures. The button-cell model is applied to evaluate how mixed ionic-electronic conductivity influences the performance of an SOFC MEA with a GDC10 electrolyte sandwiched between a porous, composite Ni-GDC10 anode and a porous, composite cathode of Sm 0.5 Sr 0.5 CoO 3− δ (i.e., SSC) and GDC10. SSC properties are also derived by fitting published conductivity and oxygen non-stoichiometry measurements. Mixed conductivity of GDC10 and competing charge transfer reactions at both electrodes reduce open circuit voltages due to leakage current and buildup of defect concentrations at electrode-electrolyte interfaces. To fit polarization data, the button-cell model includes heterogeneous reaction rates for defect incorporation on the GDC10 surface along with Butler–Volmer expressions derived for competing charge transfer reaction rates from rigorous analyses assuming rate-limiting, elementary charge transfer reactions for each electrode. The calibrated MEA model can support rigorous SOFC modeling with GDC10 electrolytes over the range of conditions within a fully operating cell.

Electrochemistry↗
DOE OSTI2025

Delineating Confinement Regimes for Nafion Thin Films via Simultaneous QCM-D and Spectroscopic Ellipsometry

Proton-conducting ionomers used in electrodes of electrochemical devices form nanometer-scale films covering metallic catalyst surfaces, wherein they experience confinement and interfacial effects absent in the bulk polymer. This confinement alters the physical properties of the ionomer film, which is postulated to increase the density and is attributed to the transport limitations observed in fuel-cell electrodes. Despite studies showing reduced swelling, no systematic measurement has validated this phenomenon by demonstrating both densification and stiffening as the film gets thinner. Here, this study aims to fill this gap by reporting the humidity-driven changes in swelling, mass uptake, and density of Nafion ionomer films cast at varying thicknesses (10–320 nm) onto a gold-plated sensor. The films were simultaneously probed during humidification using spectroscopic ellipsometry (SE) and a quartz crystal microbalance with dissipation (QCM-D), which allowed for determination of the density and shear stiffness. The effects of confinement were prominently observed below ∼30 nm, with films showing increased density along with decreased swelling and mass uptake during hydration. In addition, the confined films show a negative excess volume upon initial water sorption, implying a larger proportion of absorbed water might bound to ionic groups in accord with notion of localized densification.

Espinet, Kevin B. [University of California, Berke↗
NASA NTRS1995

Nafion(TM) Coats For Electrodes In Liquid-Feed Fuel Cells

Coating or impregnation with commercially available material enables oxidation of organic liquid fuels. Nafion(TM) investigated for use in application because of known combination of desirable characteristics: It is perfluorinated, hydrophilic, proton-conducting ion-exchange polymer exhibiting relatively high thermal and electrochemical stability and not detrimental to kinetics of electrochemical processes. Available in solubilized form and used to apply stable coats to surfaces of electrodes.

Narayanan, Sekharipuram R.↗
DOE OSTI2024

A Multifunctional Isostructural Bilayer Oxygen Evolution Electrode for Durable Intermediate-Temperature Electrochemical Water Splitting

The overarching goal of the proposed research is to address SOEC’s degradation problem by advancing a new isostructural highly electrocatalytically active bilayer oxygen evolution reaction (OER) electrode, consisting of a LSCF (La 1-x Sr x Co 1-y Fe y O 3-δ ) core and a SCT (SrCo 0.9 Ta 0.1 O 3-δ ) shell, to achieve high and sustainable rate of oxygen evolution matching operating current densities without encountering delamination. To realize this goal, the project has adopted a combined experimental and theoretical approach to conduct research in the following six areas closely associated with SOPO tasks: 1) Development of electrocatalytically active bilayer oxygen electrodes (SOPO task-1) 2) Development of new symmetric three electrode cell (STEC) methodology to extract electrokinetic data of oxygen electrodes (SOPO task-2) 3) Quantification of electrokinetics of bilayer oxygen electrodes and correlation with degradation and delamination (SOPO task-2) 4) Performances of bilayer oxygen electrodes under fuel cells and electrolyzers modes (SOPO task-3) 5) Microscale modeling of oxygen electrode/electrolyte interface in solid oxide electrolysis cells (SOPO task-4) 6) Prediction of crack growth rate at oxygen electrode/electrolyte interface in solid oxide electrolysis cells (SOPO task-4)

08 HYDROGEN↗
NASA NTRS2003

Effects Of Electric Field On Hydrocarbon-Fueled Flames

It has been observed that flames are susceptible to electric fields that are much weaker than the breakdown field strength of the flame gases. When an external electric field is imposed on a flame, the ions generated in the flame reaction zone drift in the direction of the electric forces exerted on them. The moving ions collide with the neutral species and change the velocity distribution in the affected region. This is often referred to as ionic wind effect. In addition, the removal of ions from the flame reaction zone can alter the chemical reaction pathway of the flame. On the other hand, the presence of space charges carried by moving ions affects the electric field distribution. As a result, the flame often changes its shape, location and color once an external electric field is applied. The interplay between the flame movement and the change of electric field makes it difficult to determine the flame location for a given configuration of electrodes and fuel source. In normal gravity, the buoyancy-induced flow often complicates the problem and hinders detailed study of the interaction between the flame and the electric field. In this work, the microgravity environment established at the 2.2 Second Drop Tower at the NASA Glenn Research Center is utilized to effectively remove the buoyant acceleration. The interaction between the flame and the electric field is studied in a one-dimensional domain. A specially designed electrode makes flame current measurements possible; thus, the mobility of ions, ion density, and ionic wind effect can be evaluated.

Yuan, Z.-G.↗
DOE OSTI2025

The search for high-entropy fuel-cell catalysts using disorder descriptors

The transition to a hydrogen economy depends on efficient, affordable catalysts for fuel cells. Platinum—the industry standard for fuel-cell electrodes—is costly and scarce, highlighting the need for practical alternatives. High-entropy alloys offer vast compositional diversity and tunable properties that can mitigate these issues, yet their chemical complexity and configurational disorder have hindered rational discovery. Here, we introduce a data-driven framework that couples machine learning with first-principles disorder descriptors—including the entropy forming ability, disordered enthalpy-entropy descriptor, and electronic-structure similarity metrics to platinum—to predict alloy synthesizability and catalytic performance. These descriptors are applied for the first time in the context of fuel-cell catalyst discovery. The workflow rapidly screens more than 20 000 compositions and identifies several platinum-free candidates that are economically viable, readily scalable, and exhibit promising predicted activity. These results demonstrate that disorder descriptors are reliably predicted by machine learning models and can be effectively integrated into materials-discovery pipelines, accelerating innovation across complex compositional spaces.

fuel-cell catalysts↗
DOE OSTI2022

Highly Durable Fluorinated High Oxygen Permeability Ionomers for Proton Exchange Membrane Fuel Cells

For proton exchange membrane fuel cells to be cost-competitive in light- and heavy-duty vehicle applications, their Pt content in the catalyst layers needs to be lowered. However, lowering the Pt content results in voltage losses due to high local oxygen transport resistances at the ionomer–Pt interface. It is therefore crucial to use ionomers that have higher oxygen permeability than Nafion. In this paper, novel high oxygen permeability ionomers (HOPIs) are presented, with up to five times higher oxygen permeability than Nafion, synthesized by copolymerization of perfluoro-2,2-dimethyl-1,3-dioxole (PDD) with perfluoro(4-methyl-3,6-dioxaoct-7-ene) sulfonyl fluoride (PFSVE). PDD is the source of higher permeability due to its open ring structure, while PFSVE provides ionic conductivity. Optimization of PDD content and equivalent weight enables increased fuel cell performance, mainly at high current densities, where HOPIs can achieve power densities >1.25 W cm -2 and exceed the 0.8 A cm -2 U.S. Department of Energy durability target by losing only 4.5 mV, which is over six times less than 30 mV. Finally, the interactions between HOPI and SO 3 - groups with a PtCo/C catalyst are also elucidated here at a fundamental level.

25 ENERGY STORAGE↗
DOE OSTI2024

Understanding Direct-Ammonia Protonic Ceramic Fuel Cells: High-Performance in the Absence of Precious Metal Catalysts

Ammonia has received considerable attention as a promising carbon-free hydrogen carrier. At temperatures above 400 °C, NH 3 is thermodynamically unstable with respect to decomposition into nitrogen and hydrogen and is, thus, suitable for direct use in solid oxide fuel cells (SOFCs) without external reforming. However, poor catalytic activity for ammonia decomposition at the moderate temperatures of protonic ceramic fuel cell (PCFC) operation has resulted in low fuel cell power output relative to operation on hydrogen and likely contributes to reported cell degradation. Here we prepared cells based on a thermodynamically robust electrolyte, a high activity cathode, and an anode with a distinctive structure to overcome challenges of poor activity and stability. Furthermore, the cells delivered peak power densities of 0.59 and 0.44 W cm –2 under H 2 and NH 3 , respectively, at 500 °C, excellent stability over a period of 200 h, and no detectable NO x in the anode exhaust gas.

25 ENERGY STORAGE↗
DOE OSTI2023

Cummins R-SOFC System Development

The overall purpose of this project was to reduce the Reversible-Solid Oxide Fuel Cell (R-SOFC) system cost by developing two technologies, an improved cell design and the incorporation of an ejector in the fuel recycle loop instead of a blower. A Simulink model of the baseline SOFC system was developed and calibrated with experimental test data. The R-SOFC system model was built by integrating GT Suite developed models of the steam generation components into the baseline Simulink SOFC system model. The ability to run the stack in SOEC operating mode was also added to the model. The system model was used to explore the ability of the R-SOFC system to meet operational constraints on Steam/Carbon ratio and H2 concentration on the fuel side electrode. A CFD ejector model was developed and used to explore a range of ejector design parameters, leading to the final ejector design that was prototyped for testing. A prototype steam ejector was first tested in a laboratory environment using room temperature air. The steam ejector was subsequently tested using the full hot recycle loop with all relevant heat exchangers and steam generation components. The test conditions utilized temperatures, pressures, and flow rates expected in an R-SOFC application. Throughout the experimental testing work, ejector performance test data was used to improve and then validate the CFD ejector model. A CFD cell model was developed and used to optimize thermal gradients, voltage, and cost of a new cell substrate design. A CFD comparison of co-flow and cross-flow cell designs informed the decision to use a co-flow design for the new cell substrate. Multiple rounds of CFD simulation were used to improve the cell design to minimize the variation in air and fuel distribution across cell channels and to minimize the variation in air and fuel distribution across different cells in the stack. A few prototypes of the new cell substrate design were produced and validated in a laboratory environment by thermally spraying and verifying that they met established manufacturing specifications. The cell manufacturing process was adjusted in order to bring these metrics within acceptable tolerances. Cummins’ internal calculations show that the new cell design reduces cost ~50% compared to the baseline cell, while the ejector + superheater/boiler concept reduces cost of the recycle loop by ~40%. The impact of these cost reductions on the cost of producing H2 will depend on the specific system where they are applied. Therefore, a Techno-Economic Analysis was completed using system cost as a variable, and showing how the NREL Current and Future system costs translate into H2 production cost.

Henrichsen, Lars↗