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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Fictitious phase separation in Li layered oxides driven by electro-autocatalysis

Layered oxides widely used as lithium-ion battery electrodes are designed to be cycled under conditions that avoid phase transitions. Although the desired single-phase composition ranges are well established near equilibrium, operando diffraction studies on many-particle porous electrodes have suggested phase separation during delithiation. Notably, the separation is not always observed, and never during lithiation. These anomalies have been attributed to irreversible processes during the first delithiation or reversible concentration-dependent diffusion. However, these explanations are not consistent with all experimental observations such as rate and path dependencies and particle-by-particle lithium concentration changes. Here, we show that the apparent phase separation is a dynamical artefact occurring in a many-particle system driven by autocatalytic electrochemical reactions, that is, an interfacial exchange current that increases with the extent of delithiation. We experimentally validate this population-dynamics model using the single-phase material L ix (Ni 1/3 Mn 1/3 Co 1/3 )O 2 (0.5 < x < 1) and demonstrate generality with other transition-metal compositions. Operando diffraction and nanoscale oxidation-state mapping unambiguously prove that this fictitious phase separation is a repeatable non-equilibrium effect. We quantitatively confirm the theory with multiple-datastream-driven model extraction. More generally, our study experimentally demonstrates the control of ensemble stability by electro-autocatalysis, highlighting the importance of population dynamics in battery electrodes (even non-phase-separating ones).

36 MATERIALS SCIENCE↗
DOE OSTI2025

Tantalum-stabilized ruthenium oxide electrocatalysts for industrial water electrolysis

The iridium oxide (IrO 2 ) catalyst for the oxygen evolution reaction used industrially (in proton exchange membrane water electrolyzers) is scarce and costly. Although ruthenium oxide (RuO 2 ) is a promising alternative, its poor stability has hindered practical application. Here, we used well-defined extended surface models to identify that RuO 2 undergoes structure-dependent corrosion that causes Ru dissolution. Tantalum (Ta) doping effectively stabilized RuO 2 against such corrosion and enhanced the intrinsic activity of RuO 2 . In an industrial demonstration, Ta-RuO 2 electrocatalyst exhibited stability near that of IrO 2 and had a performance decay rate of ~14 microvolts per hour in a 2800-hour test. At current densities of 1 ampere per square centimeter, it had an overpotential 330 millivolts less than that of IrO 2 .

Zhang, Jiahao [Sichuan Univ., Chengdu (China); Uni↗
DOE OSTI2022

Vapor Deposition Process for Engineering of Dispersed PEMFC ORR Pt/NbO x /C Catalysts

With support from the Department of Energy, and in partnership with Oak Ridge National Laboratory, Exothermics, Northeastern University, the University of Michigan, and IRD Fuel Cells, Ford has led an effort to use physical vapor deposition (PVD) to produce oxygen reduction reaction (ORR) catalysts for proton exchange membrane fuel cells (PEMFCs). Conventional ORR catalysts are made by wet chemical processes, and experience loss of electrochemical surface area and activity over voltage cycling due to Pt dissolution and Pt particle coalescence. Not only was PVD processing researched as a means to reduce solvent waste and enhance reproducibility in catalyst manufacturing, but it was also perceived as a means to deposit preferential phases of niobium oxide onto the catalyst, which would then serve to prevent Pt particle movement and extend PEMFC lifetime.

08 HYDROGEN↗
DOE OSTI2025

Stable Metal–Organic Electrocatalysts for Anion-Exchange Membrane Water Electrolyzers by Defect Engineering

Developing efficient and durable catalysts for the alkaline oxygen evolution reaction (OER) is vital to achieving practical anion-exchange membrane water electrolyzers (AEMWE) for green hydrogen production. In this work, we break the activity-stability trade-off of electrocatalysis by defect engineering of Ni-based metal-organic electrocatalysts (Ni-benzene dicarboxylate; Ni-BDC) through coordinating ferrocenecarboxylates (Fc) to the metal sites. Experimental results collectively reveal that the defect MOF (Ni-BDC:Fc_5:1) exhibits a high OER turnover frequency of 0.75 O 2 s -1 at 300 mV overpotential. Operando Raman spectroscopy and isotope-labelling electrochemical mass spectrometry measurements indicate the structure of Ni-BDC:Fc_5:1 is also more stable in service than that of pure Ni-BDC. The high activity and stability could be attributed to the moderate defects (i.e., unsaturated Ni sites) in the structure that not only increase the intrinsic activity and stability of the local active environment by inhibiting lattice oxygen exchange, but also electrochemically activates the bulk of the catalysts by creating a porous network that facilitates internal H 2 O/OH - conduction with enhanced electronic conduction. Accordingly, an AEMWE employing Ni-BDC:Fc_5:1 as the OER catalyst delivers an industrial-level current density of 1 A cm -2 at 1.73 V cell and can be steadily operated for more than 120 hours.

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

Recent developments in Pt–Co catalysts for proton-exchange membrane fuel cells

Development of Pt-based oxygen reduction reaction catalysts with high efficiency and high durability is central to the application of proton-exchange membrane fuel cell systems. Pt–Co bimetallic catalysts have drawn extensive attention owing to their capability of delivering high performance and long lifetime for fuel cell applications including light-duty and heavy-duty vehicles. However, further improvements in durability and performance are needed to meet market requirements. To fully exploit the potential of Pt–Co catalysts, new insights into the relationship between catalyst properties and fuel cell performance and durability are needed, and more effective methods to tailor the features of Pt–Co catalysts need to be developed. This review provides a summary and perspective on recent efforts, including work on customizing the Pt shell and Pt:Co ratio, tailoring the crystal structure, and improving carbon support properties, with a particular emphasis on mechanisms leading to enhancement of mass activity, power density, and durability in membrane electrode assembly testing.

25 ENERGY STORAGE↗
DOE OSTI2026

Tantalum oxide stabilized molybdenum-doped ruthenium oxide electrocatalysts for PEM water electrolysis

Proton exchange membrane (PEM) water electrolysis offers key advantages, including high current density, high efficiency, and compact system architecture for hydrogen production. However, its widespread implementation is limited by the scarcity and high cost of Ir-based anodic catalysts. Herein, we report an Ir-free electrocatalyst for the acidic oxygen evolution reaction (OER): tantalum oxide (TaO x )–coated molybdenum-doped RuO 2 (TaO x -MoRuO 2 ). The catalyst exhibits a low overpotential of 180 mV at 10 mA cm -2 and excellent durability, with a degradation rate of 0.034 mV h -1 over a 150-hour test at 50 mA cm -2 —surpassing other Ru-based catalysts evaluated under similar conditions. A PEM electrolyzer employing TaO x -MoRuO 2 as the anode maintained stable operation for 100 hours at 500 mA cm -2 . In conclusion, the TaO x coating layer suppresses Ru and Mo dissolution, thus enhancing their stability likely via interfacial electronic reconfiguration of Ru and Mo mediated by bridging oxygen atoms.

Durability↗
DOE OSTI2025

Open-source library for performance-portable neutrino reaction rates: Application to neutron star mergers

A realistic and detailed description of neutrinos in binary neutron star (BNS) mergers is essential to build reliable models of such systems. To this end, we present bns_nurates, a novel open-source numerical library designed for the efficient on-the-fly computation of neutrino interactions, with particular focus on regimes relevant to BNS mergers. bns_nurates targets a higher level of accuracy and realism in the implementation of commonly employed reactions by accounting for relevant microphysics effects on the interactions, such as weak magnetism and mean field effects. It also includes the contributions of inelastic neutrino scattering off electrons and positrons and (inverse) nucleon decays. Finally, it offers a way to reconstruct the neutrino distribution function in the framework of moment-based transport schemes. As a first application, we compute both energy-dependent and energy-integrated neutrino emissivities and opacities for conditions extracted from a BNS merger simulation with m1 transport scheme. We find some qualitative differences in the results when considering the impact of the additional relevant reactions and of microphysics effects. For example, neutrino-electron/positron scattering reactions are important for the energy exchange of heavy-type neutrinos as they do not undergo semileptonic charged-current processes, when μ± are not accounted for. Moreover, weak magnetism and mean field effects can significantly modify the contribution of β processes for electron-type (anti)neutrinos, increasing at the same time the importance of (inverse) neutron decays. Here, the improved treatment for the reaction rates also modifies the conditions at which neutrinos decouple from matter in the system, potentially affecting their emission spectra.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2026

Assessing the Impacts of Conformational Fluxionality on Copper(II/I) Electron Transfer Self-Exchange

Typical Cu(II/I) complexes exhibit hallmark structural changes during their electron transfer (ET) reactions that result from the (pseudo) Jahn-Teller distortions and changes in polarizability inherent to their d 10 / d 9 configurations. Given that such structural changes incur large reorganization energy penalties, slow the rates of ET are characteristic of these compounds. Notwithstanding, we recently reported a set of Cu(II/I) complexes that undergo significant and well-defined structural changes during their redox reactions yet exhibit rapid (> 10 5 M ‒1 s ‒1 ) ET self-exchange rate constants ( k 11 ). To explain these results we proposed a pre-equilibrium model in which inherent conformational fluxionality in one of the two oxidation states provides access to pathways involving lower reorganization energies during the ET event. Herein we report our results testing this hypothesis through the preparation and study of a homologous series of compounds exhibiting varying extents of con-formational fluxionality in the Cu(I) state. We characterize these compounds electrochemically, structurally, and by varia-ble temperature NMR spectroscopy to provide experimental evidence for increase fluxionality across the series. We then correlate the trend with increasing k 11 through NMR linewidth broadening experiments, further taking care to define the impacts of solvent impurities therein. Finally, the nature of the conformational rearrangements, and their relation to increased k 11 are explored computationally to reveal differential Boltzmann populations of conformers across the series. The cumulative results of these studies support a previously underappreciated strategy for overcoming barriers to slow ET kinetics: via the incorporation of conformational fluxionality.

Singh, Aditi↗
DOE OSTI2021

Influence of Heterointerfaces on the Kinetics of Oxygen Surface Exchange on Epitaxial La 1.85 Sr 0.15 CuO 4 Thin Films

Considerable attention has been directed to understanding the influence of heterointerfaces between Ruddlesden–Popper (RP) phases and ABO 3 perovskites on the kinetics of oxygen electrocatalysis at elevated temperatures. Here, we report the effect of heterointerfaces on the oxygen surface exchange kinetics by employing heteroepitaxial oxide thin films formed by decorating LaNiO 3 (LNO) on La 1.85 Sr 0.15 CuO 4 (LSCO) thin films. Regardless of LNO decoration, tensile in-plane strain on LSCO films does not change. The oxygen surface exchange coefficients (kchem) of LSCO films extracted from electrical conductivity relaxation curves significantly increase with partial decorations of LNO, whereas full LNO coverage leads to the reduction in the kchem of LSCO films. The activation energy for oxygen exchange in LSCO films significantly decreases with partial LNO decorations in contrast with the full coverage of LNO. Optical spectroscopy reveals the increased oxygen vacancies in the partially covered LSCO films relative to the undecorated LSCO film. We attribute the enhanced oxygen surface exchange kinetics of LSCO to the increased oxygen vacancies by creating the heterointerface between LSCO and LNO.

25 ENERGY STORAGE↗
DOE OSTI2020

Combining Computational Modeling with Reaction Kinetics Experiments for Elucidating the In Situ Nature of the Active Site in Catalysis

Microkinetic modeling based on density functional theory (DFT) derived energetics is important for addressing fundamental questions in catalysis. The quantitative fidelity of microkinetic models (MKMs), however, is often insufficient to conclusively infer the mechanistic details of a specific catalytic system. Here, this can be attributed to a number of factors such as an incorrect model of the active site for which DFT calculations are performed, deficiencies in the hypothesized reaction mechanism, inadequate consideration of the surface environment under reaction conditions, and intrinsic errors in the DFT exchange-correlation functional. Despite these limitations, we aim at developing a rigorous understanding of the reaction mechanism and of the nature of the active site for heterogeneous catalytic chemistries under reaction conditions. By achieving parity between experimental and modeling outcomes through robust parameter estimation and by ensuring coverage-consistency between DFT calculations and MKM predictions, it is possible to systematically refine the mechanistic model and, thereby, our understanding of the catalytic active site in situ.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Kinetic Parameters and Diffusivity of Uranium in FLiNaK and ClLiK

Anodic stripping voltammetry (ASV) and cyclic voltammetry (CV) measurements at 773, 823, and 873 K were made of uranium trifluoride (UF 3 ) in lithium fluoride-sodium fluoride-potassium fluoride eutectic (FLiNaK) and uranium trichloride (UCl 3 ) in lithium chloride-potassium chloride eutectic (ClLiK). ASV data were used to estimate the charge transfer coefficients, exchange current densities, and activation energies of the uranium reactions. Charge transfer coefficients of both salt systems were within the range of 0.17 to 0.38. Exchange current densities in the fluoride and chloride salts were estimated within the range of 0.060 to 0.12 A cm -2 . Activation energy of uranium exchange current was 16.0 kJ mol -1 in the fluoride salt and 28.9 kJ mol -1 in the chloride salt. Kinetics of charge transfer were found to be faster in FLiNaK. Analyses of the CV data suggest the electrochemical system was diffusion controlled and irreversible in the chloride and fluoride salt mixtures. Diffusion coefficients of uranium in the range of temperatures were on the order of 10-5 cm 2 s -1 in both systems. Greater values of diffusivity in ClLiK are attributed to its lower density compared with FLiNaK. Activation energy of uranium diffusion in the fluoride and chloride salt mixtures were 53.4 and 89.4 kJ mol -1 , respectively.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

Measurement of the photon beam asymmetry in γ → p → K + Σ 0 at E γ = 8.5 GeV

We report measurements of the photon beam asymmetry $\Sigma$ for the reaction $\vec{\gamma} p\to K^+\Sigma^0$(1193) using the GlueX spectrometer in Hall D at Jefferson Lab. Data were collected using a linearly polarized photon beam in the energy range of 8.2-8.8 GeV incident on a liquid hydrogen target. The beam asymmetry $\Sigma$ was measured as a function of the Mandelstam variable $t$, and a single value of $\Sigma$ was extracted for events produced in the $u$-channel. These are the first exclusive measurements of the photon beam asymmetry $\Sigma$ for the reaction in this energy range. For the $t$-channel, the measured beam asymmetry is close to unity over the $t$-range studied, $-t=(0.1-1.4)~$(GeV/$c$)$^{2}$, with an average value of $\Sigma = 1.00\pm 0.05$. This agrees with theoretical models that describe the reaction via the natural-parity exchange of the $K^{*}$(892) Regge trajectory. A value of $\Sigma = 0.41 \pm 0.09$ is obtained for the $u$-channel integrated up to $-u=2.0$~(GeV/$c$)$^{2}$.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Spin-dependent electron transfer in electrochemically transparent van der Waals heterostructures for oxygen evolution reaction

Spin selective catalysis is an emerging approach for improving the thermodynamics and kinetics of reactions. The role of electron spins has been scarcely studied in catalytic reactions. One exception is the oxygen evolution reaction (OER) where strongly correlated metals and oxides are used as catalysts. In OER, spin alignment facilitates the transition of singlet state of the reactant to the triplet state of O 2 . However, the influence of strong correlations on spin exchange mechanism and spin selective thermodynamics of most catalytic reactions remain unclear. Here we decouple the strongly correlated catalyst from the electrolyte to study spin exchange in two-dimensional (2D) magnetic iron germanium telluride (FGT) heterostructure. We demonstrate that transmission of spin and electrochemical information between the catalyst and the reactant can occur through quantum exchange interaction despite the catalyst of FGT being completely encapsulated by graphene or hexagonal boron nitride (hBN). The strong correlations in FGT that lead to enhanced spin exchange in OER are observed in graphene or hBN layers with thicknesses of up to 6 nm. We demonstrate that spin alignment in FGT leads to a lowering of thermodynamic barrier for adsorption of hydroxide ion and electron transfer to the catalyst. This results in up to fivefold enhancement in OER performance and improved kinetics. Our results provide clear evidence that transmission of both quantum mechanical and electrochemical information through quantum spin exchange interaction in FGT leads to an enhancement in catalytic performance.

2D materials↗
DOE OSTI2020

Single Cobalt Sites Dispersed in Hierarchically Porous Nanofiber Networks for Durable and High-Power PGM-Free Cathodes in Fuel Cells

Increasing catalytic activity and durability of atomically dispersed metal–nitrogen–carbon (M–N–C) catalysts for the oxygen reduction reaction (ORR) cathode in proton-exchange-membrane fuel cells remains a grand challenge. In this study, a high-power and durable Co–N–C nanofiber catalyst synthesized through electrospinning cobalt-doped zeolitic imidazolate frameworks into selected polyacrylonitrile and poly(vinylpyrrolidone) polymers is reported. The distinct porous fibrous morphology and hierarchical structures play a vital role in boosting electrode performance by exposing more accessible active sites, providing facile electron conductivity, and facilitating the mass transport of reactant. The enhanced intrinsic activity is attributed to the extra graphitic N dopants surrounding the CoN 4 moieties. The highly graphitized carbon matrix in the catalyst is beneficial for enhancing the carbon corrosion resistance, thereby promoting catalyst stability. The unique nanoscale X-ray computed tomography verifies the well-distributed ionomer coverage throughout the fibrous carbon network in the catalyst. The membrane electrode assembly achieves a power density of 0.40 W cm –2 in a practical H 2 /air cell (1.0 bar) and demonstrates significantly enhanced durability under accelerated stability tests. The combination of the intrinsic activity and stability of single Co sites, along with unique catalyst architecture, provide new insight into designing efficient PGM-free electrodes with improved performance and durability.

25 ENERGY STORAGE↗
DOE OSTI2022

Flexible Copper Metal Circuits via Desktop Laser Printed Masks

A novel process is demonstrated that produces patterns of electrically conductive copper on a flexible polyimide film substrate using standard desktop laser printed toner and near room temperature aqueous chemistry. The laser toner acts as a mask to selectively block the ion exchange self-metallization (IESM) reduction reaction that forms nanoscale silver or palladium coatings at the polyimide surface. The silver or palladium IESM coating is then used as a catalyst for electroless deposition of copper. Under appropriate conditions, the copper is deposited selectively on top of the catalyst layer. The resulting copper layer has a measured sheet resistance as low as 0.3 Ohms/sq. Electrical isolation was measured between copper traces spaced as close as 300 microns, and high conductivity was measured along traces with widths as low as 200 microns. The minimum pattern size appears to be limited primarily by the resolution of the laser toner pattern, as the IESM metal layer was observed to follow the contours of individual toner particles. Here, the process avoids the use of high temperature, vacuum, and organic solvents and is thus suitable for very low cost prototyping or distributed manufacturing of simple electronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Oxygen and Proton Transport in Flooded Graphene Pores with N-Dopants and Defects

Reactant transport is an important consideration in the design of ideal electrode structures. For the oxygen reduction reaction catalyzed by Pt/C in proton exchange membrane fuel cell cathodes, O 2 and H + delivery to Pt surfaces and H 2 O transport away are required. Some Pt nanoparticles may only be accessible via micropores that are too small for ionomer molecules to enter, possibly requiring flooding for H + transport. Here, to test if these “buried” Pt particles can play a role in activity through this proposed transport mechanism, we have performed atomic-scale simulations based on reactive force field molecular dynamics with an emphasis on confinement below 20 Å. Diffusion coefficients as a function of the molar concentration and local environment have been evaluated in water domains confined in two-dimensional graphene nanochannels of various channel heights representing a morphological model for micropores in proton exchange fuel cell cathodes. Our study shows that local atomic-scale structures can strongly modify H + , O 2 , and H 2 O transport rates in flooded micropores less than 20 Å in size. We find that there is a critical crossover in diffusion behavior around the 20 Å spacing with larger pores having bulk-like diffusion properties and confinement below 20 Å monotonically decreases diffusion rates. As pore size decreases, we observe locally dispersed water regions that ultimately strand reactants from long-distance transport. These findings suggest that flooded micropores may in fact be viable transport pathways for relevant reactants and products if the pore walls on opposite sides remain separated by ≥10 Å separation. Furthermore, the confinement effect is so strong that N-doping and C-vacancy defects in the C pore wall have only a minimal impact on diffusion rates and their effects are counterintuitively more apparent at larger spacings. These findings provide valuable insight regarding cathode performance and the role “stranded” catalyst particles may play in fuel cell cathodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Toward Chemical Accuracy for Chemi- and Physisorption with an Efficient Density Functional

Understanding molecular adsorption on surfaces underpins many problems in chemistry and materials science. Accurately and efficiently describing the adsorption has been a challenging task for first-principles methods as the process can involve both short-range chemical bond formations and long-range physical interactions, e.g., van der Waals (vdW) interaction. Density functional theory presents an appealing choice for modeling adsorption reactions, although calculations with many exchange-correlation density functional approximations struggle to accurately describe both chemical and physical molecular adsorptions. Here, we propose an efficient density functional approximation that is accurate for both chemical and physical adsorption by concurrently optimizing its semilocal component and the long-range vdW correction against the prototypical adsorption CO/Pt(111) and Ar 2 binding energy curve. The resulting function opens the door to accurate and efficient modeling of general molecular adsorption.

adsorption↗