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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Structure and Oxygen Evolution Activity of β-NiOOH: Where Are the Protons?

Ni oxides and oxyhydroxides (NiO x ) have been studied for a long time as cathode materials for alkaline batteries and electrocatalysts for the oxygen evolution reaction (OER). Yet, understanding of the connection between their atomic and electronic structures and electrochemical performance or stability is still incomplete. In this work, we use first-principles density functional theory (DFT) calculations to revisit the structure, electronic properties, and OER activity of β-NiOOH, the catalytically active phase of NiO x . Following extensive DFTbased screening, we identify a hitherto overlooked structure characterized by a uniform distribution of H atoms on the NiO 2 layers. All the Ni 3+ cations in this structure exhibit an identical t g 6 e g 1 electronic configuration with an occupied 3d z2 orbital. Comparison of the calculated bond lengths with extended X-ray absorption fine structure (EXAFS) data unequivocally supports this structure relative to all other low-energy configurations. Based on this structure, we uncover and detail defect-dominated OER mechanisms on the basal β-NiOOH (001) surface, with overpotentials as low as 0.39 V. The present results should provide a valuable contribution to ongoing efforts for understanding and developing enhanced transition-metal hydroxide catalysts for the OER.

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

Impact of Processing on Structural and Compositional Evolution in Mixed Metal Halide Perovskites during Film Formation

Understanding crystallization processes and their pathways in metal-halide perovskites is of crucial importance as this strongly affects the film microstructure, its stability, and device performance. While many approaches are developed to control perovskite formation, the mechanisms of film formation are still poorly known. Using time-resolved in situ grazing incidence wideangle X-ray scattering, the film formation of perovskites is investigated with average stoichiometry Cs 0.15 FA 0.85 PbI 3 , where FA is formamidinium, using the popular antisolvent dropping and gas jet treatments and this is contrasted with untreated films. i) The crystallization pathways during spin coating, ii) the subsequent postdeposition thermal annealing, and iii) crystallization during blade coating are studied. The findings reveal that the formation of a nonperovskite FAPbI 3 phase during spin coating is initially dominant regardless of the processing and that the processing treatment (e.g., antisolvent dropping, gas jet) has a significant impact on the as-cast film structure and affects the phase evolution during subsequent thermal treatment. It is shown that blade coating can be used to overcome the nonperovskite phase formation via solvothermal direct crystallization of perovskite phase. This work shows how real-time investigation of perovskite formation can help to establish processing–microstructure–functionality relationships.

36 MATERIALS SCIENCE↗
DOE OSTI2024

A Finite Difference informed Random Walk solver for simulating radiation defect evolution in polycrystalline structures with strongly inhomogeneous diffusivity

Diffusivity of species and defects on grain boundaries is usually several orders of magnitude larger than that inside grains. Such strongly inhomogeneous diffusivity requires prohibitively high computational demands for modeling microstructural evolution. Here, this paper presents a highly-efficient numerical solver, combining the Finite Difference method and Random Walk model, designed for accurately modeling strongly inhomogeneous diffusion within polycrystalline structures. The proposed solver, termed Finite Difference informed Random Walk (FDiRW), integrates a customized Finite Difference (cFD) scheme tailored for fast diffusion along thin grain boundaries represented by a single-layer of nodes. Numerical experiments demonstrate that the FDiRW solver achieves an impressive efficiency gain of 1560x compared to traditional Finite Difference methods while maintaining accuracy, making it feasible for personal computer machines to handle diffusional systems with strongly inhomogeneous diffusivity across static polycrystalline microstructures. The model has been successfully applied to simulate radiation defect evolution, showcasing its scalability to engineering scales in both length and time dimensions.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Evolution of Pore Structure in Organic-Lean and Organic-Rich Mudrocks

The pore structure of mudrocks is a key characteristic to evaluate flow behavior through these rocks. Although significant advances have been made to resolve pore characteristics, porosity evolution, or pore connectivity, there is still insufficient knowledge linking porosity evolution to flow and transport in mudrocks. To better understand these links, we conducted very small-angle (VSANS) and small-angle neutron scattering (SANS) experiments on 13 sets of mudrocks from global locations, characterized by differences in composition, maturity, and depositional environment. Our results indicate that a homogeneous pore structure reflects a stable and low-energy depositional environment. Organic-lean mudrocks mainly contain pores <10 nm, which restricts flow and is beneficial for, e.g., caprock seal integrity. Increasing maturity as a result of increasing burial depth, and therefore, temperature leads to porosity evolution. In organic-rich mudrocks (ORMs), this happens through the generation of organic matter pores and pore preservation around diagenetically formed carbonates. ORMs mainly contain macropores (>50 nm), favoring production from, e.g., unconventional reservoirs. SANS-derived pore size distributions will help to better understand fluid imbibition and flow properties in mudrocks through comprehensive quantitative characterization of the nano- to micron scale pore network conduits and their relationships to burial diagenesis.

58 GEOSCIENCES↗
DOE OSTI2022

A structural description of the evolution of stakeholders and risk communication in the Department of Energy's defense nuclear facilities: Historical perspective, major stakeholders, and external events

Regulators and policymakers are routinely challenged with explaining complex concepts concerning risk. Part of the challenge is helping external and internal stakeholders to understand the context behind risk-related information and decisions. Here, this paper will describe the historical evolution of the safety and regulatory framework for an important category in the nuclear industry—defense nuclear facilities owned and operated by the US Department of Energy. In parallel with describing this evolution, three major events which occurred external to the complex of defense nuclear facilities will be summarized, and their impact on the maturation of the Department's safety and regulatory framework will be discussed. Finally, integrated with these two threads of discussion will be a chronicle of the changing set of involved organizations and the expanding set of external stakeholders involved in risk decisions—and therefore, the risk communications ecosystem surrounding defense nuclear facilities. It will be noted that this system was once describable as a classic “iron triangle,” but now has progressed to a complex network of federal and state organizations, numerous congressional committees, and expanding sets of external stakeholders. It is hoped that a comprehensive discussion of the context of risk assessment in the defense nuclear facilities complex—addressing historical insights, organizational evolution, and the maturing structure of regulation—will provide enhanced opportunities for building trust and understanding in this complex environment.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
DOE OSTI2022

Beware of fake ν ’s: The effect of massive neutrinos on the nonlinear evolution of cosmic structure

Massive neutrinos suppress the growth of cosmic structure on small, nonlinear scales. It is thus often proposed that using statistics beyond the power spectrum can tighten constraints on the neutrino mass by extracting additional information from these nonlinear scales. We study the information content regarding neutrino mass at the field level, quantifying how much of this information arises from the difference in nonlinear evolution between a cosmology with one fluid [cold dark matter (CDM)] and two fluids ( CDM + neutrinos ). We do so by running two N -body simulations, one with and one without massive neutrinos, both with the same phases, and matching their linear power spectrum at a given low redshift. This effectively isolates the information encoded in the linear initial conditions from the nonlinear cosmic evolution. We demonstrate that, for k ≲ 1 h / Mpc , and for a single redshift, there is negligible difference in the real-space CDM field between the two simulations. This suggests that all the information regarding neutrino mass is in the linear power spectrum set by the initial conditions. Thus, any probe based on the CDM field alone will have negligible constraining power beyond that which exists at the linear level over the same range of scales. Consequently, any probe based on the halo field will contain little information beyond the linear power. We find similar results for the matter field responsible for weak lensing. We also demonstrate that there may be much information beyond the power spectrum in the 3D matter field; however, this is not observable in modern surveys via dark matter halos or weak lensing. Finally, we show that there is additional information to be found in redshift space.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Structural and Chemical Evolution of Highly Fluorinated Li‐Rich Disordered Rocksalt Oxyfluorides as a Function of Temperature

Abstract Li‐rich disordered rocksalt (DRS) oxyfluorides have emerged as promising high‐energy cathode materials for lithium‐ion batteries. While a high level of fluorination in DRS materials offers performance advantages, it can only be achieved via mechanochemical synthesis, which poses challenges of reproducibility and scalability. The definition of relationships between fluorination and structural stability is required to devise alternative methods that overcome these challenges. In this study, the thermal evolution of three highly fluorinated phases, Li 2 TMO 2 F (TM = Mn, Co, and Ni), is investigated in an inert atmosphere. Diffraction and spectroscopic techniques are utilized to examine their electronic and chemical states up until conditions of decomposition. The analysis reveals that the materials phase‐separate above 400 °C, at most. It is also observed that heat‐treated DRS materials exhibit intricate changes in the local coordination of the metals, including their spin, and ordering compared to the pristine states. The changes upon annealing are accompanied by a modulation of the voltage profile, including reduced hysteresis, when used as electrodes. These results provide an in‐depth understanding of the fundamental crystal chemistry of DRS oxyfluorides in view of their promising role as the next generation of Li‐ion cathodes.

25 ENERGY STORAGE↗
DOE OSTI2021

Evolution of eggshell structure in relation to nesting ecology in non-avian reptiles

Amniotic eggs are multifunctional structures that enabled early tetrapods to colonize the land millions of years ago, and are now the reproductive mode of over 70% of all terrestrial amniotes. Eggshell morphology is at the core of animal survival, mediating the interactions between embryos and their environment, and has evolved into a massive diversity of forms and functions in modern reptiles. These functions are critical to embryonic survival and may serve as models for new antimicrobial and/or breathable membranes. However, we still lack critical data on the basic structural and functional properties of eggs, particularly of reptiles. Here, we first characterized egg shape, shell thickness, porosity, and mineralization of eggs from 91 reptile species using optical images, scanning electron microscopy, and micro computed tomography, and collected data on nesting ecology from the literature. We then used comparative analyses to test hypotheses on the selective pressures driving their evolution. We hypothesized that eggshell morphology has evolved to protect shells from physical damage and desiccation, and, in support, found a positive relationship between thickness and precipitation, and a negative relationship between porosity and temperature. Although mineralization varied extensively, it was not correlated with nesting ecology variables. Ancestral state reconstructions show thinning and increased porosity over evolutionary time in squamates, but the opposite in turtles and crocodilians. Egg shape, size, porosity and calcification were correlated, suggesting potential structural or developmental tradeoffs. This study provides new data and insights into the morphology and evolution of reptile eggs, and raises numerous questions for additional research.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Orange carotenoid proteins: structural understanding of evolution and function

Cyanobacteria uniquely contain a primitive water-soluble carotenoprotein, the orange carotenoid protein (OCP). Nearly all extant cyanobacterial genomes contain genes for the OCP or its homologs, implying an evolutionary constraint for cyanobacteria to conserve its function. Genes encoding the OCP and its two constituent structural domains, the N-terminal domain, helical carotenoid proteins (HCPs), and its C-terminal domain, are found in the most basal lineages of extant cyanobacteria. These three carotenoproteins exemplify the importance of the protein for carotenoid properties, including protein dynamics, in response to environmental changes in facilitating a photoresponse and energy quenching. Furthermore, we review new structural insights for these carotenoproteins and situate the role of the protein in what is currently understood about their functions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Understanding Structural and Compositional Evolution during NMC Cathode Direct Recycling via Solid-State NMR

Recycling end-of-life lithium-ion batteries (LIBs) to recover high-value cathode materials such as LiNixMnyCozO2 (NMC) is driven by economical, geopolitical, and sustainability needs. There has been recent interest in direct recycling methods to improve efficiency and recovery of materials, including ionothermal, hydothermal, solid-state, or redox mediator methods. In conjunction with recycling process development, detailed structural characterization is necessary in order to understand the mechanisms and efficacy of cathode recycling steps. Solid-state nuclear magnetic resonance (NMR) spectroscopy is a unique tool that can probe Li coordination, bulk and surface environments, and transition metal ordering in recycled and upcycled NMC cathodes. Here, 6,7Li, 1H, and 19F NMR spectroscopy to probe structural and compositional changes as well as surface impurities that may form during each step in NMC direct recycling is utilized. During relithiation, Li reinsertion into the NMC lattice is observed. During upcycling, where the goal is to increase the Ni content in the NMC, incorporation of Ni-rich phases into the bulk Li environment is observed. Surface impurities formed during processing were also identified. These studies provide valuable information for optimizing recycling processes to reach targeted cathode composition and structure that can enable electrochemical performance comparable to or better than pristine materials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Structural and chemical evolution in layered oxide cathodes of lithium-ion batteries revealed by synchrotron techniques

Abstract Rechargeable battery technologies have revolutionized electronics, transportation and grid energy storage. Many materials are being researched for battery applications, with layered transition metal oxides (LTMO) the dominating cathode candidate with remarkable electrochemical performance. Yet, daunting challenges persist in the quest for further battery developments targeting lower cost, longer lifespan, improved energy density and enhanced safety. This is, in part, because of the intrinsic complexity of real-world batteries, featuring sophisticated interplay among microstructural, compositional and chemical heterogeneities, which has motivated tremendous research efforts using state-of-the-art analytical techniques. In this research field, synchrotron techniques have been identified as a suite of effective methods for advanced battery characterization in a non-destructive manner with sensitivities to the lattice, electronic and morphological structures. This article provides a holistic overview of cutting-edge developments in synchrotron-based research on LTMO battery cathode materials. We discuss the complexity and evolution of LTMO’s material properties upon battery operation and review recent synchrotron-based research works that address the frontier challenges and provide novel insights in this field. Finally, we formulate a perspective on future directions of synchrotron-based battery research, involving next-generation X-ray facilities and advanced computational developments.

25 ENERGY STORAGE↗
DOE OSTI2022

Resolving atomistic structure and oxygen evolution activity in nickel antimonates

The oxygen evolution reaction (OER) requires electrodes that are not only catalytically active, but also stable under harsh electrochemical environments to enable efficient, durable technologies. Our recent report of a stable amorphous Ni 0.5 Sb 0.5 O z OER photoanode established Ni–Sb–O as an important system for computational understanding of both the structural and catalytic behavior of these complex oxides. In the present work we show that Ni x Sb 1-x O z with x > 0.33 crystallizes into a previously unknown phase. Guided by experimental X-ray diffraction, here, we use density functional theory calculations to perform a prototype phase search to identify a broad family of stable and metastable mixed rutile and hexagonal-like phases for x = 0.33, 0.50, and 0.66 compositions. For the identified phases, we predict favorable oxygen vacancy formation energies for Ni-rich compositions under the reducing synthesis conditions which match measured Ni K-edge X-ray absorption spectra. The calculated overpotential for the most active site decreases with increasing Ni content, from 0.91 V (x = 0.33) to 0.49 V (x = 0.66), which captures the experimentally observed trend. We find the active site changes from the Ni–O–Sb bridge to a Ni–O–Ni bridge at increasing Ni concentrations, rather than the commonly studied singly under-coordinated sites. Finally, detailed Pourbaix analysis of the identified phases show excellent electrochemical stability, consistent with experimentally measured low metal ion concentrations in the electrolyte of photoelectrochemical cells. Collectively, our consideration of an ensemble of structures enables identification of the most catalytically prolific structural motifs, aiding the understanding of crystalline and amorphous catalysts and elucidating the co-optimization of activity and durability in nickel antimonates.

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

Evolution of Pore Structure and Permeability of Rocks Under Hydrothermal Conditions (Final Report)

The physical and transport properties of porous rocks can be altered by a variety of diagenetic, metamorphic, and tectonic processes, and the changes that result are of critical importance to such industrial applications as resource recovery, carbon dioxide sequestration, and waste isolation in geologic formations. The associated interrelationships between rocks, pore fluids and deformation are also key to understanding many natural processes, including dynamic metamorphism, fault mechanics, fault stability and pressure solution creep. In this project, we investigated the changes of permeability and pore geometry owing to inelastic deformation by solution-transfer, brittle fracturing and dislocation creep. In particular, we studied the coupling between pore fluids and deformation in fluid-filled quartz, calcite, mudstones and ultramafic rocks and examine the effects of coupled mechanical and chemical processes on the evolution of porosity and permeability under hydrothermal conditions. The investigations used a combination of techniques, that included triaxial laboratory experiments; uniaxial compressive loading with in situ observations of microstructure; permeability under hydrostatic compression; observations of microstructure using optical and electron microscopes, and micro-CT imaging; and numerical calculations. Laboratory experiments were designed to provide mechanical and transport data under conditions that isolate the particular mechanisms responsible for the changes. The data obtained were used to quantify changes in surface roughness, porosity, pore dimensions and their spatial fluctuations. The results of the experiments and data from image analyses were compared to the results of network, finite-difference and other numerical models to verify the validity of experimentally established relations between permeability and other rock properties. A bibliography for the period from 2015-2019 is appended below. New results obtained in the final year and the unfunded extension period are detailed below.

58 GEOSCIENCES↗
DOE OSTI2021

Evolution of the structure and chemical composition of the interface between multi-component silicate glasses and yttria-stabilized zirconia after 40,000 h exposure in air at 800 °C

The chemical and structural stability of two commercial multicomponent silicate glasses (SCN and G6) in contact with yttria-stabilized zirconia (YSZ) was investigated after exposure times of up to 40,000 h in air at 800 °C. With exposure time, interfacial layers develop at the SCN-YSZ and G6-YSZ interfaces, which were characterized in detail using both quantitative chemical analysis and atomic-resolution imaging. At the SCN-YSZ interface, a Ca-Ba-Si-O reaction phase was found to grow by diffusion control. In G6-YSZ, Raman spectroscopy and electron microscopy revealed a disorganized interfacial reaction later between G6 and YSZ, and the occurrence of cubic to tetragonal to monoclinic phase transformations in YSZ. Finally, this microstructural evolution is discussed in terms of devitrification resistance of glass and diffusion processes at interfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Evolution of glass structure during femtosecond laser assisted crystallization of LaBGeO 5 in glass

Single crystal LaBGeO 5 architecture formed in La 2 O 3 -B 2 O 3 -2GeO 2 glass serves as a model system for understanding of the transformation from glass to single crystal under fs laser irradiation. This transformation is highly sensitive to glass composition, raising the need to understand how the glass structure and composition evolve during crystallization. In this work, micro X-ray absorption spectroscopy and X-ray fluorescence mapping were used to study the glass structure and composition preceding LaBGeO5 crystallization in the region surrounding the single crystal growth front. The results show precipitation of germanium nanoparticles, as well as anisotropic segregation of Ge and La prior to LaBGeO5 crystallization, which are explained assuming electromigration in high fields within the plasma formed by the fs laser irradiation. However, these nanoparticles do not serve as sites for heterogeneous nucleation. Furthermore, the similarity of local structure around Ge in the starting glass and the ultimate crystal appears to enhance the crystallization process.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Structural and electrochemical evolution of alloy interfacial layers in anode-free solid-state batteries

“Anode-free” solid-state batteries feature high energy density since there is no anode active material. Although the beneficial effects of interfacial layers at the anode-solid electrolyte interface have been demonstrated, the mechanisms through which they influence lithium plating/stripping are unclear. Here, in this study, we reveal the evolution of 100-nm silver and gold interfacial layers during lithium plating/stripping using electrochemical methods, electron microscopy, X-ray microcomputed tomography, and modeling. The alloy layers improve Coulombic efficiency and resistance to short circuiting, even though the alloys form solute regions or particulates that detach from the current collector during plating. In situ electrochemical impedance spectroscopy shows that the alloys return to the interface and mitigate contact loss at the end of stripping, avoiding a critical vulnerability of anode-free cells. Contact retention is driven by even Li thickness that promotes spatially uniform stripping, as well as local alloy delithiation in response to current concentrations that homogenizes current and diminishes voiding.

25 ENERGY STORAGE↗