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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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

In Situ and Operando Observation of Zinc Moss Growth and Dissolution in Alkaline Electrolyte for Zinc–Air Batteries

As a promising battery technology, zinc–air batteries still face significant challenges, including the formation of a mossy structure on the zinc metal anode in alkaline electrolyte. Because a similar phenomenon also plagues lithium and sodium metal batteries, elucidating its mechanism has important implications for progress in energy storage. Herein, operando X-ray nanotomography was employed to visualize zinc moss growth and dissolution at the individual colony level. By tracking its microstructure evolution, zinc moss was found to display irreversible plating/stripping behavior. While zinc moss exhibits self-limiting growth and zinc deposition occurs mainly in its outer region, zinc dissolution is more uniformly distributed inside the moss colony upon stripping, leading to the formation of “dead” zinc and capacity loss. A direct correlation is established between the moss amount and zinc plating/stripping efficiency. Finally, results from this study offer new insights into mitigating the unstable zinc plating morphology and improving the cycle life of aqueous zinc–air batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Comparing Intrinsic Catalytic Activity and Practical Performance of Ni- and Pt-Based Alkaline Anion Exchange Membrane Water Electrolyzer Cathodes

The stringent cost and performance requirements of renewable hydrogen production systems dictate that electrolyzers benefit from the use of nonprecious catalysts only if they deliver the same level of activity and durability as their precious metal counterparts. Here we report on recent work to understand interrelationships between the intrinsic activity of Ni- and Pt-based electrolyzer cathode catalysts and their performance in zero-gap alkaline water electrolyzer assemblies. Our results suggest that nanoparticulate Ni–Mo exhibits HER activity that is roughly 10-fold lower than Pt–Ru on the basis of turnover frequency under low (≤100 mV) polarization conditions. We further found that the HER activity of Ni–Mo/C cathodes is inhibited by aryl piperidinium anionexchange ionomers bearing bicarbonate counter-anions. After addressing this poisoning effect, we produced electrolyzer assemblies based on Ni–Mo/C cathodes that delivered indistinguishable current density vs cell potential relationships compared to otherwise identical assemblies with Pt–Ru cathodes. This result indicates that the contribution of the cathode to the total cell polarization is small, even for the less active Ni–Mo/C catalyst, and further implies that Pt-based cathodes can indeed be replaced by nonprecious alternatives with no loss in performance.

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

Restoring Escaped Zincate in Rechargeable Alkaline Zinc Batteries with a Seed-in-Nanoshell Design

Rechargeable alkaline zinc batteries are promising candidates for safe and low-cost energy storage, but suffer from ZnO dissolution that causes irreversible active material loss and rapid capacity decay. Here, we report a seed-in-nanoshell ZnO anode architecture that mitigates dissolution by combining physical confinement with electrochemical restoration of dissolved zincate species. ZnO particles are encapsulated within an ion-sieving carbon nanoshell that restricts zincate diffusion, maintains electrical conductivity, and stabilizes repeated solid–solution–solid transformations. Silver (Ag) nanoparticles incorporated into the nanoshell act as zincophilic nucleation seeds, lowering the Zn deposition barrier and directing the redeposition of dissolved zincate back to metallic Zn during charging. This confinement-enabled restoration mechanism converts zincate dissolution from an irreversible loss pathway into a recoverable process, enabling improved performance under harsh test conditions. The anode also delivers 227.9 mAh g −1 at −40 °C. Finally, a scalable tens-of-gram synthesis of ZnO@Ag is demonstrated, underscoring the practical potential of this strategy for advanced aqueous zinc batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Interpenetrating 3D Electrodes for High-Rate Alkaline Water Splitting

Mass transfer is critical for the reaction kinetics and efficiency of alkaline water splitting (AWS). For AWS to operate at high current densities (hundreds of mA/cm 2 ), the device architecture must ensure a large catalytic surface area, rapid ion diffusion, and minimal solution and charge transfer resistances. Effective electrodes should also facilitate gas bubble detachment and release. 3D-printed electrodes have shown promise, but stacking them increases the ion diffusion length and solution resistance. Here we demonstrate a new device architecture with interpenetrating gyroid electrodes, providing a large ion-accessible surface area and gas diffusion channels. This design significantly reduces the interelectrode distance, lowering ion diffusion length and solution resistance. Simulations show faster ion diffusion and higher current density in the interpenetrating configuration compared with separate electrodes. This improved performance, especially at low temperatures and high current densities, highlights a promising strategy for enhancing AWS and other electrochemical systems limited by slow ion diffusion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Satellite-Dominated Sulfur L 2,3 X-ray Emission of Alkaline Earth Metal Sulfides

The sulfur L 2,3 X-ray emission spectra of the alkaline earth metal sulfides BeS, MgS, CaS, SrS, and BaS are investigated and compared with spectra calculations based on density functional theory. Very distinct spectral shapes are found for the different compounds. With decreasing electronegativity of the cation, that is, increasing ionic bonding character, the upper valence band width and its relative spectral intensity decrease. These general trends are qualitatively reproduced by the spectra calculations, which give quite an accurate description of the spectral shapes in the upper valence band region. On the low energy side of the sulfur 3s → 2p transition dominating the spectra, we find strong satellites caused by "semi-Auger" decays involving configuration interaction. These satellites, previously believed to be energetically forbidden for sulfur L 2,3 emission and only observed for the L 2,3 emission of Cl to Cr, increase in intensity as the bonding character becomes more ionic and dominate the spectra for SrS and BaS. The intensities, energies, and widths of the satellites vary strongly between the investigated compounds, giving a very specific spectral fingerprint that can be used for speciation analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Evaluation of a V 8 C 7 Anode for Oxygen Evolution in Alkaline Media: Unusual Morphological Behavior

Metallic vanadium carbide (V 8 C 7 ) with cubic symmetry is examined as an oxygen evolution reaction (OER) precatalyst in alkaline media. Herein, we used quasi in situ scanning electron microscopy and energy-dispersive X-ray spectrometry to investigate the structural transformation of the precatalyst V 8 C 7 microparticles during extended cyclic voltammetric (CV) OER testing. Interestingly, an anisotropic morphological transformation (from a distorted sphere to a cuboid) of V 8 C 7 was observed. Our theoretical and experimental results strongly suggest that this morphological change happens due to the selective self-oxidation and dissolution of the V 8 C 7 (110) and (111) surfaces and the subsequent exposure of the relatively stable (100), (010), and (001) surfaces. Lastly, these results also suggest that these stable facets are preferable for the OER, and a current density of 10 mA·cm –2 was delivered at an overpotential of 503 mV after the extended CV OER testing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Cation Crossover Limits Accessible Current Densities for Zero-Gap Alkaline CO2 Reduction to Ethylene

Traditional CO2 reduction systems often fail in an alkaline environment due to the interaction of CO2 with a high-pH electrolyte, where carbonate and bicarbonate ion formation results in potassium-containing salt precipitation. The presence of the salt crystals causes a reduction in the selectivity of the electrolyzer toward CO2 conversion. Here, the critical operational variables, which elicit the salting out process, are investigated (i.e., ion transport). When the electrolyzer exceeds a critical current density, H2 evolution dominates CO2 reduction due to salt formation, which is confirmed by postmortem cross-sectional SEM-EDS of the electrode. The critical current density decreases with an increasing membrane thickness or anolyte ionic strength. Cathode salt formation is mediated by the unmitigated crossover of cations from the anolyte to the cathode across an anion exchange membrane, through which cations are imperfectly excluded. It is likely that electric field-driven migration promotes an increase in concentration of potassium across the membrane, until, at the critical current density for that electrolyzer arrangement, the concentration of potassium and bicarbonate ions exceeds the solubility limit of KHCO3, leading to salt precipitation.

CO2 reduction↗
DOE OSTI2020

Hydrogen Stabilized RhPdH 2D Bimetallene Nanosheets for Efficient Alkaline Hydrogen Evolution

The design of catalysts with high activity and robust stability for alkaline hydrogen evolution reaction (HER) remains a great challenge. Here, we report an efficient catalyst of two-dimensional bimetallene hydrides, in which H atoms stabilize the rhodium palladium bimetallene. The system exists because of the introduction of H that is in-situ chemically released from the formaldehyde solution during the synthesis. This provides a highly stable catalyst based on an unstable combination of metal elements. Density functional theory calculations show the H is confined by electronic interactions and the Miedema rule of reverse stability of the RhPd alloy.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Oxidative Catalytic Fractionation of Lignocellulosic Biomass under Non-alkaline Conditions

Biomass pretreatment methods are commonly used to isolate carbohydrates from biomass, but they often lead to modification, degradation, and/or low yields of lignin. Catalytic fractionation approaches provide a possible solution to these challenges by separating the polymeric sugar and lignin fractions in the presence of a catalyst that promotes cleavage of the lignin into aromatic monomers. In this work, we demonstrate an oxidative fractionation method conducted in the presence of a heterogeneous non-precious-metal Co-N-C catalyst and O 2 in acetone as the solvent. The process affords a 15 wt% yield of phenolic products bearing aldehydes (vanillin, syringaldehyde) and carboxylic acids (p-hydroxybenzoic acid, vanillic acid, syringic acid), complementing the alkylated phenols obtained from existing reductive catalytic fractionation methods. The oxygenated aromatics derived from this process have appealing features for use in polymer synthesis and/or biological funneling to value-added products, and the non-alkaline conditions associated with this process support preservation of the cellulose, which remains insoluble at reaction conditions and is recovered as a solid.

09 BIOMASS FUELS↗
DOE OSTI2024

Atomically Dispersed Zn/Co–N–C as ORR Electrocatalysts for Alkaline Fuel Cells

Hydrogen fuel cells have drawn increasing attention as one of the most promising next-generation power sources for future automotive transportation. Developing efficient, durable, and low-cost electrocatalysts, to accelerate the sluggish oxygen reduction reaction (ORR) kinetics, is urgently needed to advance fuel cell technologies. Herein, we report on metal–organic frameworks-derived nonprecious dual metal single-atom catalysts (SACs) (Zn/Co–N–C), consisting of Co–N 4 and Zn–N 4 local structures. These catalysts exhibited superior ORR activity with a half-wave potential (E 1/2 ) of 0.938 V versus RHE (reversible hydrogen electrode) and robust stability (ΔE 1/2 = –8.5 mV) after 50k electrochemical cycles. Moreover, this remarkable performance was validated under realistic fuel cell working conditions, achieving a record-high peak power density of ~1 W cm –2 among the reported SACs for alkaline fuel cells. Operando X-ray absorption spectroscopy was conducted to identify the active sites and reveal catalytic mechanistic insights. The results indicated that the Co atom in the Co–N 4 structure was the main catalytically active center, where one axial oxygenated species binds to form an O ads –Co–N 4 moiety during the ORR. In addition, theoretical studies, based on a potential-dependent microkinetic model and core-level shift calculations, showed good agreement with the experimental results and provided insights into the bonding of oxygen species on Co–N 4 centers during the ORR. Furthermore, this work provides a comprehensive mechanistic understanding of the active sites in the Zn/Co–N–C catalysts and will pave the way for the future design and advancement of high-performance single-site electrocatalysts for fuel cells and other energy applications.

25 ENERGY STORAGE↗
DOE OSTI2023

Hybrid Iodide Perovskites of Divalent Alkaline Earth and Lanthanide Elements

Hybrid halide perovskites AM II X 3 (A = ammonium cation, M II = divalent cation, X = Cl, Br, I) have been extensively studied but have only previously been reported for the divalent carbon group elements Ge, Sn, and Pb. While they have displayed an impressive range of optoelectronic properties, the instability of Ge II and Sn II and the toxicity of Pb have stimulated significant interest in finding alternatives to these carbon group-based perovskites. Here, we describe the low-temperature solid-state synthesis of five new hybrid iodide perovskites centered around divalent alkaline earth and lanthanide elements, with the general formula AM II I 3 (A = methylammonium, MA; M II = Sr, Sm, Eu, and A = formamidinium, FA; M II = Sr, Eu). Structural, calorimetric, optical, photoluminescence, and magnetic properties of these materials are reported.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Contrasting Responses of Soil Inorganic Carbon to Afforestation in Acidic Versus Alkaline Soils

Afforestation is recommended as an effective approach for carbon sequestration and environmental benefits. However, it remains less clear, and sometimes controversial, regarding how afforestation may impact soil inorganic carbon (SIC), a crucial component of the ecosystem carbon pool. Here, using field data from 619 afforested plots and 163 control plots across northern China, we investigated the relative and absolute differences in SIC between afforested and corresponding control plots. Our results suggested that afforestation increased SIC in acidic soils, while decreased SIC in alkaline soils. Fitting a linear mixed model and further a structure equation model, we found that afforestation-induced soil pH change was the most significant factor regulating SIC responses. In particular, SIC was more sensitive to pH change in more arid areas, where both soil pH and SIC stocks were high. Other factors could indirectly affect SIC responses to afforestation through modulating soil pH and soil organic carbon (SOC) dynamics. Moreover, afforestation-induced SIC changes also varied considerably among different species of tree plantations and across different soil depths. Importantly, in plantations of Pinus sylvestris var. mongholica, Pinus tabuliformis, and Populus spp., changes in SIC caused by afforestation were even comparable to that in SOC. Overall, our findings provide a data-based understanding on the comprehensive soil carbon dynamics following afforestation and its underlying mechanisms. With the increased use of afforestation and reforestation as nature-based solutions to climate change, their associated impacts on SIC need to be taken into account, especially in SIC-rich areas.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Determining hexavalent chromium transport properties in alkaline nuclear waste using nuclear magnetic resonance spectroscopy

This study focuses on the transport properties of hexavalent chromium, specifically the chromate anion, to improve predictive models and environmental remediation strategies for Cr(VI) migration. Using 53 Cr Nuclear Magnetic Resonance (NMR) spectroscopy, the research quantifies chromate in multicomponent electrolytes replicating nuclear waste conditions at the Hanford Site in Washington State. The consistency of the 53 Cr NMR signal integral with chromate concentration, despite varying matrix compositions, establishes it as a reliable concentration indicator. The transport properties of chromate in an alkaline solution were assessed using relaxation-based measurements via saturation recovery and Carr-Purcell-Meiboom-Gill experiments, determining spin-lattice and spin-spin relaxation times. These measurements, combined with the Bloembergen-Purcell-Pound equation, helped estimate the rotational correlation time and the 53 Cr self-diffusion coefficient using Stokes-Einstein-Debye and Stokes-Einstein equations. Direct measurements were obtained through pulsed field gradient stimulated echo 53 Cr NMR spectroscopy. Monte Carlo simulations further estimated uncertainty propagation. The results enhance comprehension of chromate transport and highlight prospects for identifying transport properties of NMR-active nuclei, traditionally considered unreachable.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Enhanced stability of silicon for photoelectrochemical water oxidation through self-healing enabled by an alkaline protective electrolyte

Alkaline electrolytes impede the corrosion of Si photoanodes under positive potentials and/or illumination, due to the formation of a SiO x layer that etches 2–3 orders of magnitude more slowly than Si. Hence during water oxidation under illumination, pinholes in protection layers on Si photoanodes result in the local formation of a protective, stabilizing passive oxide on the Si surface. However, operation under natural diurnal insolation cycles additionally requires protection strategies that minimize the dark corrosive etching rate of Si at pinholes. We show herein that addition of [Fe(CN) 6 ] 3- to 1.0 M KOH(aq) results in a self-healing process that extends the lifetime to >280 h of an np + -Si(100) photoanode patterned with an array of Ni catalyst islands operated under simulated day/night cycles. The self-healing [Fe(CN) 6 ] 3- additive caused the exposed Si(100) surface to etch >180 times slower than the Si etch rate in 1.0 M KOH(aq) alone. No appreciable difference in etch rate or facet preference was observed between Si(100) and Si(111) surfaces in 1.0 M KOH(aq) with [Fe(CN) 6 ] 3- , indicating that the surface conformally oxidized before Si dissolved. The presence of [Fe(CN) 6 ] 3- minimally impacted the faradaic efficiency or overpotential of p + -Si/Ni electrodes for the oxygen-evolution reaction.

25 ENERGY STORAGE↗
DOE OSTI2021

Investigations of the stability of etched or platinized p-InP(100) photocathodes for solar-driven hydrogen evolution in acidic or alkaline aqueous electrolytes

Here, the stability of p-InP photocathodes performing the hydrogen-evolution reaction (HER) has been evaluated in contact with either 1.0 M H 2 SO 4 (aq) or 1.0 M KOH(aq), with a focus on identifying corrosion mechanisms. Stability for the solar-driven HER was evaluated using p-InP electrodes that were either etched or coated with an electrodeposited Pt catalyst (p-InP/Pt). Variables such as trace O 2 were systematically controlled during the measurements. Changes in surface characteristics after exposure to electrochemical conditions as well as electrode dissolution processes were monitored using X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometry (ICP-MS). In either H 2 SO 4 or KOH, etched p-InP photoelectrodes corroded cathodically under illumination, forming metallic In 0 at the electrode surface. In contrast, electrodeposition of Pt kinetically stabilized illuminated p-InP photocathodes in both H 2 SO 4 and KOH by inhibiting the cathodic corrosion pathway. Notably, when held at 0 V vs. the reversible hydrogen electrode (RHE) in 1.0 M H 2 SO 4 (aq), p-InP/Pt exhibited a stable current density (J) of ~–18 mA cm –2 for >285 h under simulated 1 Sun illumination. The long-term current density vs. potential (J–E) behavior at pH 0 and pH 14 of p-InP/Pt photocathodes correlated with changes in the surface chemistry as well as the dissolution of p-InP. In acidic media, the J–E behavior of p-InP/Pt photocathodes remained nearly constant with time, but the surface of a p-InP/Pt electrodes gradually turned P-rich via a slow and continuous leaching of In ions. In alkaline electrolyte, the surface of p-InP/Pt electrodes was passivated by formation of an InO x layer that exhibited negligible dissolution but led to a substantial degradation in the J–E characteristics. Consequently, changes in the catalytic kinetics and surface stoichiometry are both important considerations for determining the corrosion chemistry and the long-term operational stability of InP photoelectrodes.

14 SOLAR ENERGY↗