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DOE OSTI2026

Reaction Diffusion Modelling of 3D Pillar Electrodes in Single-Catalyst CO 2 Reduction Cascades

Effective electrochemical CO 2 reduction to liquid fuels requires that the local catalytic environment facilitates the desired reactivity, yet a microscopic understanding of this environment is difficult to achieve from experiment alone. In this work, a 3D reaction-diffusion model was developed to explore the effects of electrode surface area and local geometry on the performance of a heterogeneous catalyst that performs a two-step CO 2 reduction cascade reaction to CO and then CH 3 OH under aqueous conditions. Kinetic parameters for the model were inspired by experimental results using a cobalt phthalocyanine (CoPc) catalyst. Three-dimensional architectures composed of arrays of square pillars with varying dimensions and either smooth or periodically modulated surfaces were tested, revealing the extent to which geometry modulates the performance of the cascade reactions. Although structural variations modulate local concentration gradients, we find that electrochemically active surface area predominantly governs the overall cascade reaction. Moreover, the results suggest that supersaturation of CO, with concentrations up to ten-fold higher than the equilibrium solubility limit, might be critical for more efficient conversion to CH 3 OH. For any given geometry, the spatially averaged ratio of [CO] to [CO 2 ] is dictated by the electrochemically active surface area and determines the yield of CH 3 OH. For a fixed surface area, geometries that spatially confine the electrolyte yield moderate local [CO] to [CO 2 ] ratios within small volumes. In contrast, less confining geometries result in a broader distribution of local ratios spread over larger volumes, with both configurations yielding the same spatially averaged [CO] to [CO 2 ] ratio. These insights provide valuable design principles—highlighting the critical importance of surface area and possibly CO supersaturation—for engineering advanced electrode architectures that leverage intermediate trapping and CO supersaturation to enhance overall performance in tandem CO 2 reduction systems.

COMSOL↗

DOE OSTI2022

Continuum Modeling of Porous Electrodes for Electrochemical Synthesis

Electrochemical synthesis possesses substantial promise to utilize renewable energy sources to power the conversion of abundant feedstocks to value-added commodity chemicals and fuels. Of the potential system architectures for these processes, only systems employing 3-D structured porous electrodes have the capacity to achieve the high rates of conversion necessary for industrial scale. However, the phenomena and environments in these systems are not well understood and are challenging to probe experimentally. Fortunately, continuum modeling is well-suited to rationalize the observed behavior in electrochemical synthesis, as well as to ultimately provide recommendations for guiding the design of next-generation devices and components. In this review, we begin by presenting an historical review of modeling of porous electrode systems, with the aim of showing how past knowledge of macroscale modeling can contribute to the rising challenge of electrochemical synthesis. We then present a detailed overview of the governing physics and assumptions required to simulate porous electrode systems for electrochemical synthesis. Here, leveraging the developed understanding of porous-electrode theory, we survey and discuss the present literature reports on simulating multiscale phenomena in porous electrodes in order to demonstrate their relevance to understanding and improving the performance of devices for electrochemical synthesis. Lastly, we provide our perspectives regarding future directions in the development of models that can most accurately describe and predict the performance of such devices and discuss the best potential applications of future models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2004

Micro-Tubular Fuel Cells

Micro-tubular fuel cells that would operate at power levels on the order of hundreds of watts or less are under development as alternatives to batteries in numerous products - portable power tools, cellular telephones, laptop computers, portable television receivers, and small robotic vehicles, to name a few examples. Micro-tubular fuel cells exploit advances in the art of proton-exchange-membrane fuel cells. The main advantage of the micro-tubular fuel cells over the plate-and-frame fuel cells would be higher power densities: Whereas the mass and volume power densities of low-pressure hydrogen-and-oxygen-fuel plate-and-frame fuel cells designed to operate in the targeted power range are typically less than 0.1 W/g and 0.1 kW/L, micro-tubular fuel cells are expected to reach power densities much greater than 1 W/g and 1 kW/L. Because of their higher power densities, micro-tubular fuel cells would be better for powering portable equipment, and would be better suited to applications in which there are requirements for modularity to simplify maintenance or to facilitate scaling to higher power levels. The development of PEMFCs has conventionally focused on producing large stacks of cells that operate at typical power levels >5 kW. The usual approach taken to developing lower-power PEMFCs for applications like those listed above has been to simply shrink the basic plate-and-frame configuration to smaller dimensions. A conventional plate-and-frame fuel cell contains a membrane/electrode assembly in the form of a flat membrane with electrodes of the same active area bonded to both faces. In order to provide reactants to both electrodes, bipolar plates that contain flow passages are placed on both electrodes. The mass and volume overhead of the bipolar plates amounts to about 75 percent of the total mass and volume of a fuel-cell stack. Removing these bipolar plates in the micro-tubular fuel cell significantly increases the power density.

Kimble, Michael C.↗

DOE OSTI2020

Solvent–Solvent Correlations across Graphene: The Effect of Image Charges

Wetting experiments show pure graphene to be weakly hydrophilic, but its contact angle (CA) also reflects the character of the supporting material. Measurements and Molecular Dynamics simulations on suspended and supported graphene often reveal a CA reduction due to the presence of the supporting substrate. A similar reduction is consistently observed when graphene is wetted from both sides. The effect has been attributed to transparency to molecular interactions across the graphene sheet, however, the possibility of substrate-induced graphene polarization has also been considered. Computer simulations of CA on graphene have so far been determined by ignoring the material’s conducting properties. We improve the graphene model by incorporating its conductivity according to the Constant Applied Potential Molecular Dynamics. Using this method, we compare the wettabilities of suspended graphene and graphene supported by water by measuring the CA of cylindrical water drops on the sheets. The inclusion of graphene conductivity and concomitant polarization effects lead to a lower CA on suspended graphene but the CA reduction is significantly bigger when the sheets are also wetted from the opposite side. The stronger adhesion is accompanied by a profound change in the correlations among water molecules across the sheet. While partial charges on water molecules interacting across an insulator sheet attract charges of the opposite sign, apparent attraction among like charges is manifested across the conducting graphene. The change is associated with graphene polarization, as the image charges inside the conductor attract equally signed partial charges of water molecules on both sides of the sheet. Additionally, by using a non-polar liquid (diiodomethane), we affirm a detectable wetting translucency when liquid-liquid forces are dominated by dispersive interactions. Furthermore, our findings are important for predictive modeling toward a variety of applications including sensors, fuel cell membranes, water filtration, and graphene-based electrode materials in high-performance supercapacitors.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2022

Anion-exchange membranes with internal microchannels for water control in CO 2 electrolysis

Electrochemical reduction of carbon dioxide (CO 2 R) poses substantial promise to convert abundant feedstocks (water and CO 2 ) to value-added chemicals and fuels using solely renewable energy. However, recent membrane-electrode assembly (MEA) devices that have been demonstrated to achieve high rates of CO 2 R are limited by water management within the cell, due to both consumption of water by the CO 2 R reaction and electro-osmotic fluxes that transport water from the cathode to the anode. Additionally, crossover of potassium (K + ) ions poses concern at high current densities where saturation and precipitation of the salt ions can degrade cell performance. Herein, a device architecture incorporating an anion-exchange membrane (AEM) with internal water channels to mitigate MEA dehydration is proposed and demonstrated. A macroscale, two-dimensional continuum model is used to assess water fluxes and local water content within the modified MEA, as well as to determine the optimal channel geometry and composition. The modified AEMs are then fabricated and tested experimentally, demonstrating that the internal channels can both reduce K + cation crossover as well as improve AEM conductivity and therefore overall cell performance. This work demonstrates the promise of these materials, and operando water-management strategies in general, in handling some of the major hurdles in the development of MEA devices for CO 2 R.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

High-Platinum-Content Catalysts on Atomically Dispersed and Nitrogen Coordinated Single Manganese Site Carbons for Heavy-Duty Fuel Cells

Fuel cells for heavy-duty vehicles (HDVs) have attracted considerable attention because of their unique scalability, better fuel economy, the less demand for hydrogen refilling infrastructure. However, the potential application requires more stringent fuel cell durability up to 25,000 h. Membrane electrode assemblies (MEAs) made from platinum group metal (PGM) catalyst with relatively high loading 0.3 mgPt cm –2 play a crucial role in ensuring high-power and long-term durability. Integrating fine PGM nanoparticles and robust carbon support with strengthened interactions is critical for improving MEA performance and durability. Herein, a unique atomically dispersed and nitrogen coordinated single Mn site-rich carbon (M–N–C) support was developed for high content (40 wt%) platinum catalysts for the oxygen reduction reaction (ORR) cathode with reduced thickness. Compared with two controls studied in this work (e.g., a porous graphitic carbon-supported Pt and a commercial TKK Pt/C catalysts), the Pt (40 wt%)/Mn–N–C catalyst exhibited much enhanced catalytic activity and stability for the ORR in both aqueous acidic electrolyte and polymer electrolyte-based MEA. Here, we carefully elucidated the—role of the Mn–N–C support in promoting Pt catalyst concerning its high surface area, partially graphitic structure, and nitrogen dopants, providing better Pt nanoparticle dispersion, and strengthened interactions between Pt and carbon. Consequently, the MEA from the Pt (40 wt%)/Mn–N–C catalyst generated a 1.61 A cm –2 at 0.7 V based on HDV conditions (0.2 mgPt cm –2 and 250 kPa air). More importantly, the MEA is highly durable and can retain 1.31 A cm –2 at 0.7 V after 30,000 voltage cycles (~19% loss), surpassing the commercial Pt/C catalyst (loss of ~56%). Therefore, the Mn–N–C carbon-supported Pt catalyst holds a great promise to meet the challenging DOE target (1.07 A cm –2 at 0.7 V after 150,000 cycles) for HDVs.

25 ENERGY STORAGE↗

NASA NTRS1972

A model to predict the degradation of a SiGe thermopile.

Discussion of the various phenomena which affect the available output power of a typical radioisotope thermoelectric generator (RTG), including estimates of the magnitude of these effects. Power degradation, as well as the corresponding changes in operating temperature, are calculated by means of a computer code which systematically accounts for the time- and temperature-dependent variables. A model for predicting available output power of an RTG is developed which includes changes in performance due to fuel decay, alteration of bulk thermoelectric properties, changes in electrode contacts, geometry changes due to material sublimation, and degradation of the thermal insulation.

Stapfer, G.↗

DOE OSTI2024

Electrochemical Imaging of Precisely‐Defined Redox and Reactive Interfaces

Abstract Understanding the diverse electrochemical reactions occurring at electrode‐electrolyte interfaces (EEIs) is a critical challenge to developing more efficient energy conversion and storage technologies. Establishing a predictive molecular‐level understanding of solid electrolyte interphases (SEIs) is challenging due to the presence of multiple intertwined chemical and electrochemical processes occurring at battery electrodes. Similarly, chemical conversions in reactive electrochemical systems are often influenced by the heterogeneous distribution of active sites, surface defects, and catalyst particle sizes. In this mini review, we highlight an emerging field of interfacial science that isolates the impact of specific chemical species by preparing precisely‐defined EEIs and visualizing the reactivity of their individual components using single‐entity characterization techniques. We highlight the broad applicability and versatility of these methods, along with current state‐of‐the‐art instrumentation and future opportunities for these approaches to address key scientific challenges related to batteries, chemical separations, and fuel cells. We establish that controlled preparation of well‐defined electrodes combined with single entity characterization will be crucial to filling key knowledge gaps and advancing the theories used to describe and predict chemical and physical processes occurring at EEIs and accelerating new materials discovery for energy applications.

Edgecomb, Joseph↗

DOE OSTI2024

Electrochemical Imaging of Precisely‐Defined Redox and Reactive Interfaces

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Challenges and strategies for probing the composite interface of PEM electrolyzers and fuel cells using operando AP-XPS

Left: cross-section schematic of a membrane electrode assembly, the working electrode changing state with applied potential. Center: the operando cell design that enables snapshot data acquisition during trajectory movement. Right: resulting spectra. Understanding the surface chemistry of electrocatalyst systems under operando conditions is central to revealing the electrocatalytic cell's working mechanisms. Determination of these catalytic processes on a molecular scale and the involved components is fundamental to streamlining material design for energy conversion and storage applications. X-ray photoelectron spectroscopy (XPS) is an established technique used to study the chemical and electronic states of materials. While the surface sensitivity of XPS is typically high, use of tender X-ray energies and technical advancements have allowed for the direct probing of solid–vapor and solid–liquid interfaces. However, protocols and documentation of experimental considerations for operando XPS probing of working electrolyzers and fuel cells remain scarce. Herein, we report an approach for the study of working polymer electrolyte membrane (PEM) electrolysis cells using ambient pressure X-ray photoelectron spectroscopy (AP-XPS). This approach directly probes the composite electrode surface on the membrane electrode assembly (MEA) in 100% relative humidity to establish a meaningful liquid layer for electrocatalysis. We carry out a systematic investigation from the cell constituent components to a fully assembled working operando electrolytic system and establish a method for AP-XPS study of the complex composite MEA, providing recommendations for data acquisition and component analysis.

Hamlyn, Rebecca↗

NASA NTRS1983

Electrocatalysis of fuel cell reactions: Investigation of alternate electrolytes

Oxygen reduction and transport properties of the electrolyte in the phosphoric acid fuel cell are studied. A theoretical expression for the rotating ring-disk electrode technique; the intermediate reaction rate constants for oxygen reduction on platinum in phosphoric acid electrolyte; oxygen reduction mechanism in trifluoromethanesulfonic acid (TFMSA), considered as an alternate electrolyte for the acid fuel cells; and transport properties of the phosphoric acid electrolyte at high concentrations and temperatures are covered.

Chin, D. T.↗

DOE OSTI2022

On-Demand Designing of Cathode Internal Surface Architecture for Dramatic Enhancement of SOFC Performance and Durability

This project is aimed to design and modify the internal surfaces of porous composite cathode from currently commercially viable Solid Oxide Fuel Cells (SOFCs), using additive manufacturing process of Atomic Layer Deposition (ALD). The material systems being investigated are commercial composite electrodes complex three-dimensional topographies. In term of the chemistry of the ALD layer applied on the internal surface of the porous cathode, this project has employed commercially relevant electrolyte, electrocatalyst and noble metal materials set. Such materials are fully compatible with the commercial fuel cells, and this project has developed special nanostructure on the surface of the commercial composite cathodes. The formation of the designed nanoarchitecture on the surface of SOFC cathode has been achieved through precise control of ALD parameters and their effect on overall cell performance and resultant electrochemical reaction mechanism of cathodes has been investigated through full cell electrochemical performance testing and nanostructure characterization by transmission electron microscopy (TEM). Under the support of this award, following has been achieved: (1). For cathode materials in solid oxide fuel cells (SOFCs), such as perovskite mixed conductor La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-x (LSCF), cation surface segregation and consequently losing conductivity and active sites for the oxygen reduction reaction (ORR) are problematic. To mitigate the cation segregation and enhance SOFC durability, further decorating the internal backbone surface using the desired electrocatalysts could be a promoting approach. Commonly, the cation segregation such as Sr is very volatile, so the effective surface decoration is ideally conformal. Nevertheless, the conformal surface coating would inevitably alter the ORR pathways that initially take place on the surface of the backbone. To reveal the impact of the conformal coating on both the catalytic activity and the conductivity of the cathode, the unary electrocatalyst of Pt or CoO x , was applied to the LSCF/SDC composite electrode of inherently functional SOFCs, respectively. Both ALD coating layers evolve strong interaction with the LSCF composite cathode. Upon operations, the Pt coating layer remains conformal on LSCF grain surfaces but turns into discrete particles on SDC grain surfaces. Meanwhile, CoO x conformal coating grows to be the discrete nanograins on both the LSCF and SDC grains. ALD coating of the cathode alone reduces the ohmic resistance up to 28 % for the entire cells. The increased conductivity induced by the ALD coating of Pt or CoO x is ascribed to different mechanisms. For the inherent functional SOFCs, the present study presents a novel and feasible approach to apply a conformal, dense coating layer on the surface of a mixed conductor, simultaneously increasing the conductivity and durability of the SOFC cathode. (2). High resistance of the oxygen electrode still significantly hinders the state-of-the-art Solid Oxide Fuel Cells (SOFCs). In particular, for an oxygen electrode consisting of mixed electronic and ionic conductors, such as perovskite lanthanum strontium cobalt ferrite (LSCF), it deteriorates due to its low chemical stability of the grain surface. Such degradation is often associated with the segregation of cations. To prevent the cation surface segregation and its resultant perovskite phase decomposition, we demonstrate a conformal ultra-thin (7-10 nm) surface heterogeneous coating layer consisting of subjacent discrete Pt nanoparticles capped with a superjacent fully dense conformal CoO x layer. The performance studies indicate the ALD coating reduces the cell series resistance by up to 40 %. The conformal CoO x layer consists of randomly orientated but single-layered nanograins, with high-density intergranular and surface grain boundaries serving as the electrochemical reaction sites and facilitating mass transport. The conformal coating layer appears to have successfully suppressed the Sr outward diffusion and confined the Sr enriched layer to a ~ 2 nm interface perovskite phase between the coating layer and the LSCF grain surface. Moreover, this ultra-thin Sr enriched perovskite layer presumably possesses high oxygen vacancy and high ionic conductivity and further imposes tensile strain to the LSCF grain surfaces. With the combination of a conformal CoO x nanoionics, Sr enriched layer, and its strained interface, the ALD coating induced surface layer is estimated to have a conductivity of ~ 1.27x10 4 S/cm, which is over two orders magnitude of that from LSCF at 750 ºC.

30 DIRECT ENERGY CONVERSION↗

DOE OSTI2023

High-performance ionomerless cathode anion-exchange membrane fuel cells with ultra-low-loading Ag–Pd alloy electrocatalysts

Rapid translation of catalysts from fundamental studies to high-performance devices could facilitate the process of developing and commercializing anion-exchange membrane fuel cells (AEMFCs). Traditionally, translation from material screening in three-electrode rotating disk electrode (RDE) cells to AEMFCs is complicated by differences in microenvironments, e.g. solid ionomer/membrane vs liquid electrolyte. Herein, we introduce a platform for translation to devices that utilizes ionomerless ultra-low-loading Ag-Pd alloy electrocatalyst cathodes synthesized by co-physical vapor deposition (PVD). Our ionomerless cathodes allow for systematic H 2 -O 2 AEMFC experiments while demonstrating comparable activity trends to those in three-electrode cells. Furthermore, here we show that our Ag 10 Pd 90 -based AEMFC reaches a peak power density of ~1 W cm$_{geo}^{-2}$ and ~10 W mg$_{PGM Cathode}^{-1}$ satisfying the U.S. Department of Energy’s platinum-group-metal (PGM) loading and cost targets. Our approach shows promise in facilitating the rapid translation between three-electrode studies and AEMFCs, offering a simple and effective design for decreasing PGM loadings.

25 ENERGY STORAGE↗

DOE OSTI2024

Lithium inventory tracking as a non-destructive battery evaluation and monitoring method

Tracking the active lithium (Li) inventory in an electrode shows the true state of a Li battery, akin to a fuel gauge for an engine. However, non-destructive Li inventory tracking is currently unavailable. Here, in this work, we used the theoretical capacity of a transition metal oxide to convert capacity into a Li inventory analysis. The Li inventory in electrodes was tracked reliably to show how battery formulations and test methods affect performance. Contrary to capacity, Li inventory tracking reveals stoichiometric variations near the electrode–electrolyte interface. Verifiable results rationalized differences in measurements, clarifying and reducing interferences from cell formulations and experimental manipulations. By tracing four variables from formation to end-of-life, we characterize electrode and cell performance with a thermodynamic framework. Accurate rationalization of subtle differences in Li inventory utilization promises precise battery engineering, evaluation, failure analysis and risk mitigation. The method could be applicable from cell design optimization and fabrication to battery management, improving battery performance and reliability.

25 ENERGY STORAGE↗

NASA NTRS1985

Long-life high performance fuel cell program

A multihundred kilowatt Regenerative Fuel Cell for use in a space station is envisioned. Three 0.508 sq ft (471.9 cm) active area multicell stacks were assembled and endurance tested. The long term performance stability of the platinum on carbon catalyst configuration suitability of the lightweight graphite electrolyte reservoir plate, the stability of the free standing butyl bonded potassium titanate matrix structure, and the long life potential of a hybrid polysulfone cell edge frame construction were demonstrated. A 18,000 hour demonstration test of multicell stack to a continuous cyclical load profile was conducted. A total of 12,000 cycles was completed, confirming the ability of the alkaline fuel cell to operate to a load profile simulating Regenerative Fuel Cell operation. An orbiter production hydrogen recirculation pump employed in support of the cyclical load profile test completed 13,000 hours of maintenance free operation. Laboratory endurance tests demonstrated the suitability of the butyl bonded potassium matrix, perforated nickel foil electrode substrates, and carbon ribbed substrate anode for use in the alkaline fuel cell. Corrosion testing of materials at 250 F (121.1 C) in 42% wgt. potassium identified ceria, zirconia, strontium titanate, strontium zirconate and lithium cobaltate as candidate matrix materials.

Martin, R. E.↗

DOE OSTI2021

An overview of bipolar plates in proton exchange membrane fuel cells

Bipolar plates are a crucial component of proton exchange membrane fuel cells. They are responsible for transporting reactant gases, carrying the current from the membrane electrode assembly to the end plates, providing heat and water management, and separating the individual cells. However, these plates also contribute to 80% of the fuel cell’s weight, 50% of its volume, and 40% of its cost, posing a barrier to the commercialization of fuel cells. This paper provides a comprehensive review of the materials and manufacturing processes used in the fabrication of bipolar plates as well as recent research conducted on the improvement of bipolar plate weight, volume, and cost through material selection and manufacturing methods. Additive manufacturing is highlighted in this work as an innovative manufacturing method to produce bipolar plates. Novel contributions in this paper include a detailed explanation of traditional manufacturing processes for metallic and graphitic-polymer bipolar plates as well as a cost comparison between additive and traditional manufacturing processes.

08 HYDROGEN↗

DOE OSTI2020

Examining Ohmic Losses in Fuel-Cell Catalyst Layers with Different Pt/C Ratios

A model of a fuel-cell cathode with distinct proton conductivities at the agglomerate and electrode scales was used to simulate polarization curves under conditions with facile oxygen transport. Here, the model was applied to electrodes containing agglomerates with different ratios of platinum to carbon in order to examine the hypothesis that intra-agglomerate proton conductivity is substantially lower than ionomer conductivity. The model predicts decreasing performance and increasing sensitivity to Pt/C ratio as intra-agglomerate conductivity declines relative to a constant through-electrode conductivity. Experiments on catalyst layers with Vulcan supports do not show the predicted trend indicating that mesoscale intra-agglomerate conductivity is not orders of magnitude lower than bulk ionomer conductivity.

08 HYDROGEN↗

DOE OSTI2021

Ultrathin platinum nanowire based electrodes for high-efficiency hydrogen generation in practical electrolyzer cells

Significant reduction of noble metal catalyst loading and simplification of electrode fabrication are urgently needed in order to lower the cost of proton exchange membrane electrolyzer cells (PEMECs) for large-scale hydrogen production. Herein, we report an integrated electrode design comprising in-situ grown platinum nanowires (PtNW) on ultrathin titanium liquid/gas diffusion layers (LGDLs) via a cost-effective and green chemical synthesis approach. The ultrathin integrated PtNW electrodes showed a low cell voltage of 1.643 V and high efficiency of 90.08% at 1000 mA cm -2 using about 15 times lower catalyst loadings than a conventional catalyst-coated membrane in PEMEC tests. Ex-situ electrochemical characterizations and microscale visualizations further reveal that PtNW electrodes display highly efficient hydrogen evolution reactions and excellent electrode durability due to high active surface area, favorable bubble detachment, and structural stability. This work provides new insights into catalyst layer design and facile ultrathin electrode fabrication for more compact and low-cost PEM electrolyzers, fuel cells and other systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗