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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Developing Materials for High-Energy-Density Solid State Li-S Batteries

Solid-state lithium-sulfur batteries are considered to be the next-generation power source for vehicle applications due to their high energy density (up to 3 times more than current Li-ion) and low cost of sulfur (100 times less than conventional cobalt oxide). However, issues with solid-state electrolyte stability, conduction pathways in the sulfur cathode, and the interface between solid-state electrolyte and sulfur cathode must be solved in order to allow commercialization. This project demonstrates the creation of new, advanced materials which overcome these inherent issues. Current approaches based on polymer or liquid electrolyte with additives have been able to improve stability at the cost of efficiency. In contrast, by creating new hybrid materials it is possible to achieve both stability and efficiency. We developed a novel sulfide-based solid electrolyte, a sulfur-carbon composite cathode, and explored various additives to stabilize the interface of solid electrolyte and cathode. After the desired properties were achieved, these materials were integrated into a high-performance solid-state battery, bringing low-cost high-energy solid-state lithium-sulfur batteries one step closer to reality.

25 ENERGY STORAGE↗
DOE OSTI2024

Suppressing Atmospheric Degradation of Sulfide-Based Solid Electrolytes via Ultrathin Metal Oxide Layers

Sulfide-based solid-state electrolytes (SSEs) are promising materials with superior Li-ion conductivity; however, their poor atmospheric stability limits commercial manufacturing at scale. Here, we investigate the impact of ultrathin metal oxide layers deposited via atomic layer deposition (ALD) on the stability of Li 6 PS 5 Cl (LPSCl). Al 2 O 3 layers grown directly on LPSCl particles significantly stabilize the surface chemistry and Li-ion transport properties relative to uncoated material upon exposure to both an ambient atmosphere (22% relative humidity, RH) and humidified O 2 (100% RH). Detailed investigations indicate that coatings impede the surface and bulk degradation kinetics of exposed materials, even for coatings as thin as ∼1 Å. Furthermore, this suggests that stabilization is due to more than just a physical barrier. Shifts in valence band edge positions of coated LPSCl indicate that ALD coatings alter the surface electronic structure and resulting oxidation tendency of underlying LPSCl, suggesting new avenues to improving the environmental stability of sulfide SSEs.

Atmospheric chemistry↗
DOE OSTI2022

Effects of C/Mn Ratios on the Sorption and Oxidative Degradation of Small Organic Molecules on Mn-Oxides

We report manganese (Mn) oxides have a high surface area and redox potential that facilitate sorption and/or oxidation of organic carbon (OC), but their role in regulating soil C storage is relatively unexplored. Small OC compounds with distinct structures were reacted with Mn(III/IV)-oxides to investigate the effects of OC/Mn molar ratios on Mn–OC interaction mechanisms. Dissolved and solid-phase OC and Mn were measured to quantify the OC sorption to and/or the redox reaction with Mn-oxides. Mineral transformation was evaluated using X-ray diffraction and X-ray absorption spectroscopy. Higher OC/Mn ratios resulted in higher sorption and/or redox transformation; however, interaction mechanisms differed at low or high OC/Mn ratios for some OC. Citrate, pyruvate, ascorbate, and catechol induced Mn-oxide dissolution. The average oxidation state of Mn in the solid phase did not change during the reaction with citrate, suggesting ligand-promoted mineral dissolution, but decreased significantly during reactions with the other compounds, suggesting reductive dissolution mechanisms. Phthalate primarily sorbed on Mn-oxides with no detectable formation of redox products. Mn–OC interactions led primarily to C loss through OC oxidation into inorganic C, except phthalate, which was predominantly immobilized in the solid phase. Together, these results provided detailed fundamental insights into reactions happening at organo–mineral interfaces in soils.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2004

Solid oxidized fuel cells seals leakage setup and testing

As the world s reserves of fossil fuels are depleted, the U.S. Government, as well as other countries and private industries, is researching solutions for obtaining power, answers that would be more efficient and environmentally friendly. For a long time engineers have been trying to obtain the benefits of clean electric power without heavy batteries or pollution-producing engines. While some of the inventions proved to be effective (i.e. solar panels or windmills) their applications are limited due to dependency on the energy source (i.e. sun or wind). Currently, as energy concerns increase, research is being carried out on the development of a Solid Oxide Fuel Cell (SOFC). The United States government is taking a proactive role in expanding the technology through the Solid State Energy Conversion Alliance (SECA) Program, which is coordinated by the Department of Energy. into an electrical energy. This occurs by the means of natural tendency of oxygen and hydrogen to chemically react. While controlling the process, it is possible to harvest the energy given off by the reaction. SOFCs use currently available fossil fuels and convert a variety of those fuels with very high efficiency (about 40% more efficient than modem thermal power plants). At the same time they are almost entirely nonpolluting and due to their size they can be placed in remote areas. The main fields where the application of the fuel cells appears to be the most useful for are stationary energy sources, transportation, and military applications. structure and materials must be resolved. All the components must be operational in harsh environments including temperatures reaching 800 C and cyclic thermal- mechanical loading. Under these conditions, the main concern is the requirement for hermetic seals to: (1) prevent mixing of the fuel and oxidant within the stack, (2) prevent parasitic leakage of the fuel from the stack, (3) prevent contamination of the anode by air leaking into the stack, (4) electrically isolate the individual cells within the stack, and (5) mechanically bond the cell components. The sealing challenges are aggravated by the need to maintain hermetic boundaries between the different flow paths within the fuel cell throughout cycled operation. Within the timeframe of my tenure, the main objective is to assist in building a state-of-art test facility.

Bastrzyk, Marta B.↗
DOE OSTI2024

Sorption and Oxidative Degradation of Small Organic Molecules on Mn-Oxides-Effects of pH and Mineral Structures

Manganese (Mn)-oxides regulate carbon (C) cycling in soils by sorbing and oxidizing organic compounds. The composition of soil organic matter varies widely, and little is known about the reactivity of individual organic compounds with structurally diverse Mn-oxides under various environmentally relevant pH conditions. Here, in this study, we examined the affinity of six organic compounds for three Mn-oxides, comprised of layer (birnessite and hydrous Mn oxide HMO) or tunnel (cryptomelane) structures, at acidic (pH 4), slightly acidic (pH 6), and slightly alkaline (pH 8) conditions. Cryptomelane, with a higher specific surface area and point of zero charge, showed higher reactivity than that of HMO and birnessite. Interestingly, these Mn-oxides, although different in structures, decomposed each organic compound to form the same products. Citrate, pyruvate, ascorbate, and catechol induced reduction and dissolution of Mn-oxides. After the reaction, the average oxidation state of Mn in the solids was much lower at pH 4 than at pH 6 and 8, suggesting more reduction under more acidic conditions. Even when reacting with phthalate and propanol, which only sorbed to Mn-oxides but did not degrade, there was proton-promoted Mn dissolution under acidic conditions. These results suggest the significance of environmental pH and mineral structures in affecting the Mn–organic interactions and provide fundamental insights into a better understanding of the roles of Mn-oxides in regulating soil C cycling.

58 GEOSCIENCES↗
DOE OSTI2024

Characteristics of oxide-dispersion strengthened alloys produced by high-temperature severe deformation

This study is to explore an economically attractive and technically feasible processing method for oxide-nanoparticle strengthened alloys for fusion reactor application. Despite many scientific merits of the advanced oxide-dispersion strengthened (ODS) alloys, such as the nanostructured ferritic alloy (NFA) 14YWT, the only viable production path for a high-quality NFA is the high-power mechanical alloying process. This process is often a multi-day high-speed ball milling of alloy powder with a small quantity of yttria (Y 2 O 3 ) powder, followed by the milled-powder consolidation using extrusion or other methods and additional thermomechanical processing (TMP) for property control. This complex production path, including the low-temperature mechanical alloying in particular, has limited technical advancement toward the cost-effective and scale-up production of ODS alloy components. To overcome such a practical limitation, we proposed to explore alternative low-cost processing routes using traditional thermomechanical processing (TMP) method only. Further, a series of continuous TMP cycles, which were designed to impose high-temperature severe plastic deformation (HT-SPD) conditions to the consolidated powder mixtures, were applied to achieve the effective distribution of oxide particles in nanograin structure and thus desirable mechanical properties. Since the reduced-activation ferritic-martensitic (RAFM) alloy powders (Fe-10Cr and Fe-14Cr alloys with various Y contents) are available in our inventory, we focused to utilize the new solid-state synthesis approach for controlling oxide (oxygen source) dissolution and nanoscale clustering in nanograin structure in those alloys. A combination of powder consolidation at 900 °C and continuous thermomechanical activation at 600 °C yielded two essential ODS alloy microstructure contents–nanograin structure and nanoparticle distribution–and thus demonstrated a good combination of strength and ductility.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Insights into the Oxidative Degradation Mechanism of Solid Amine Sorbents for CO 2 Capture from Air: Roles of Atmospheric Water

Direct air capture (DAC) processes for extraction of CO 2 from ambient air are unique among chemical processes in that they operate outdoors with minimal feed pretreatments. Here, the impact of humidity on the oxidative degradation of a prototypical solid supported amine sorbent, poly(ethylenimine) (PEI) supported on Al 2 O 3 , is explored in detail. By combining CO 2 adsorption measurements, oxidative degradation rates, elemental analyses, solid-state NMR and in situ IR spectroscopic analysis in conjunction with 18 O labeling of water, a comprehensive picture of sorbent oxidation is achieved under accelerated conditions. Here we demonstrated that the presence of water vapor can play an important role in accelerating the degradation reactions. From the study we inferred the identity and kinetics of formation of the major oxidative products, and the role(s) of humidity. Our data are consistent with a radical mediated autooxidative degradation mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Tailoring Binder Molecular Weight to Enhance Slurry-Cast NMC Cathodes for Sulfide Solid-State Batteries

We demonstrate for the first time the critical influence of binder molecular weight on the performance of slurry-cast lithium nickel manganese cobalt oxide (NMC) cathodes in sulfide-based all-solid-state batteries (SSBs). SSBs are increasingly recognized as a safer and potentially more efficient alternative to traditional Li-ion batteries, owing to the superior ionic conductivities and inherent safety features of sulfide solid electrolytes. However, the integration of high-voltage NMC cathodes with sheet-type sulfide solid electrolytes presents significant fabrication challenges. Our findings reveal that higher molecular weight binders not only enhance the discharge capacity and cycle life of these cathodes but also ensure robust adhesion and structural integrity. By optimizing binder molecular weights, we effectively shield the active materials from degradation and mechanical stress, significantly boosting the functionality and longevity of SSBs. These results underscore the paramount importance of binder properties in advancing the practical application of high-performance all-solid-state batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Probing Interactions between Adsorbed Polymers and γ-Al 2 O 3 Using Solid-State NMR

The interactions between polymers and metal oxide surfaces affect the physical properties of polymer composites and the selectivity of catalysts used for plastic conversion. Gauging the strengths of these interactions and how they depend on adsorption conformations and polymer structure is nevertheless quite challenging. Herein, we evaluate whether a recently introduced dynamic nuclear polarization-based surface-to-atom distance measurement method can be used to gauge the specific interactions between five vinyl polymers and an oxide support (alumina). The adsorption conformations of polymer monolayers were studied using site-specific 13 C{ 27 Al} rotational-echo saturation-pulse double-resonance (RESPDOR) experiments. The method is effective in revealing the average distance between the adsorbed polymer and the surface, as well as the fraction of the monomers that are adsorbed. Polymers that possess larger side chains are more weakly adsorbed, as evidenced by their formation of more numerous loop and tail structures. In conclusion, the measured RESPDOR dephasing data further reveals that polymer adsorption conformations are largely disordered and involve few hydrogen bonding interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2007

Metal/Metal Oxide Differential Electrode pH Sensors

Solid-state electrochemical sensors for measuring the degrees of acidity or alkalinity (in terms of pH values) of liquid solutions are being developed. These sensors are intended to supplant older electrochemical pH sensors that include glass electrode structures and reference solutions. The older sensors are fragile and subject to drift. The present developmental solid-state sensors are more rugged and are expected to be usable in harsh environments. The present sensors are based on a differential-electrode measurement principle. Each sensor includes two electrodes, made of different materials, in equilibrium with the solution of interest.

West, William↗
DOE OSTI2024

Facile Interfacial Reduction Suppresses Redox Chemical Expansion and Promotes the Polaronic to Ionic Transition in Mixed Conducting (Pr,Ce)O 2−δ Nanoparticles

Mixed ionic/electronic conductors (MIECs) are essential components of solid-state electrochemical devices, such as solid oxide fuel/electrolysis cells. For efficient performance, MIECs are typically nanostructured, to enhance the reaction kinetics. However, the effect of nanostructuring on MIEC chemo-mechanical coupling and transport properties, which also impact cell durability and efficiency, has not yet been well understood. Here, in this work, Pr 0.2 Ce 0.8 O 2−δ (PCO20) nanopowders were prepared by coprecipitation, then sintered in a modified dilatometer at three different temperatures (600, 725, and 850 °C) for microstructure evolution, resulting in three samples with different average particle sizes (23, 30, and 53 nm). The chemical strain and electronic/ionic conductivity were then measured simultaneously on stable nanostructures in four isotherms from 550 to 400 °C with steps in pO 2 (1 to 10 –4 atm O 2 ). A microcrystalline bar was prepared and measured for comparison. Particle size reduction led to a monotonically decreasing isothermal redox chemical strain, confirmed by in situ high-temperature, controlled-atmosphere XRD measurements. The corresponding conductivity measurements provided defect chemical insight into the particle size-dependent chemical expansion behavior. The significant weakening of the pO 2 dependence and decreased activation energy for electrical conduction with decreasing particle size indicated a decrease in the reduction enthalpy of PCO, shifting the transition from (Pr) polaronic to ionic behavior to higher pO 2 . STEM-EELS measurements confirmed the majority of Pr was reduced to 3+ in the nanoparticles, while Ce remained 4+. These results demonstrate suppression of deleterious chemical expansion and tailoring of the dominant charge carrier simply through controlling the particle size, providing insights for MIEC microstructural design.

ceria↗
DOE OSTI2026

A structural and electrochemical study of perfluoropolyether-poly(ethylene oxide) solid polymer electrolytes

Solid polymer electrolytes offer attractive safety, processability, and interfacial adhesion for enabling high–energy solid-state lithium batteries, but they are often limited by narrow oxidative stability windows and low lithium-ion transference numbers. In an attempt to broaden the electrochemical stability window and increase lithium-ion transference number of poly(ethylene oxide) (PEO)-based solid polymer electrolytes, we produce an optically clear, crosslinked membrane of PEO and perfluoropolyether (PFPE) using a mixed solvent method and subsequently infuse the membrane with a lithium salt. Structural and thermal analyses reveal nanoscale phase separation between fluorocarbon and hydrocarbon domains with characteristic spacings of 7–8 nm and an elevated glass transition for the hydrocarbon phase. Consistent with this, PFPE-containing membranes exhibit substantially lower ionic conductivity than PEO analogs (dry and plasticized). The transference number and electrochemical stability are similar to pure PEO. These results demonstrate that fluorination implemented as segregated nanoscale domains does not deliver the anticipated transport or stability benefits; instead, phase separation increases tortuosity and suppresses hydrocarbon-phase dynamics. The work underscores the importance of fluorine placement and morphology control, guiding the design of partially fluorinated solid polymer electrolytes toward architectures that avoid detrimental nanoscale phase separation.

Carden, Peyton [ORNL] (ORCID:0000000162296538)↗
DOE OSTI2021

Thermal Processing Conditions for the Synthesis of Near Theoretical Density Li 5 La 3 Ta 2 O 12 Ceramics for Ceramic Dual-Mode Detectors

A family of Li-containing garnet compounds, extensively investigated for Li-ion solid electrolyte applications, show great potential to be developed into transparent ceramic dual-mode scintillators. In particular, Li 5 La 3 Ta 2 O 12 (LLTaO) shows promise as an efficient dual-mode scintillator due to its high Li content, high density, non-hygroscopicity, and high effective-Z. Often the synthesis of LLTaO ceramics involves solid state processing techniques starting with oxide and carbonate powders, calcining, sintering for the removal of residual porosity, and post-processing. This study focuses on two objectives: (1) establishing thermal processing boundary conditions for a flexible alkoxide-based sol-gel method for synthesizing fine-grained powders; and (2), consolidating powders via hot-pressing to form high-density ceramics. In this study, near single-phase ceramics were achieved by hot-pressing sol-gel powders with varying amounts of excess Li. Rietveld refinements were used to analyze X-ray diffraction data and provide a quantitative evaluation of the phases present in the hot pressed ceramics. Some of the diffraction data showed large low angle peak asymmetry, suggesting the presence of two cubic Li 5 La 3 Ta 2 O 12 garnet phases with different lattice parameters. Depending on the synthesis and processing conditions, the refinement revealed ~ 90 wt% concentration of a phase with a ≈ 12.8 Å and ~ 10 wt% concentration of a phase with a ≈ 12.9 Å, indicating a remaining excess of Li in the hot pressed ceramics in the large lattice parameter phase. These synthesis experiments allowed for the determination of a baseline for Li loss during hot-pressing. X-ray excited radioluminescence and photoluminescence excitation and emission spectra were obtained from the hot pressed ceramics. In conclusion, the measured emission spectra featured broad tantalate emission and line emissions likely from a rare-earth impurity.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Investigating Cu-Site Doped Cu–Sb–S Nanoparticles Using Photoelectron and Electron Paramagnetic Resonance Spectroscopy

Tetrahedrite (Cu 12 Sb 4 S 13 ) and famatinite (Cu 3 SbS 4 ) are good candidates for green energy applications because they possess promising thermoelectric and photovoltaic properties as well as contain earth-abundant and nontoxic constituents. Herein, X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and electron paramagnetic resonance spectroscopy (EPR) methods examined inherent electronic properties and interatomic magnetic interactions of Cu-site doped tetrahedrite and famatinite nanomaterials. An energy-efficient modified polyol method was utilized for the synthesis of tetrahedrite and famatinite nanoparticles doped on the Cu-site with Zn, Fe, Ni, Mn, and Co. This is the first parallel study of tetrahedrite and famatinite nanomaterials with XPS, UPS, and EPR methods alongside a systematic analysis of dopant-dependent effects on the electronic structure and magnetic interactions for each material. XPS showed that the Cu and Sb species in tetrahedrite and famatinite possess different oxidation states, while UPS characterization reveals larger dopant-dependent shifts in the work function for tetrahedrite nanoparticles (4.21 to 4.79 eV) than for famatinite nanoparticles (4.57 to 4.77 eV). Finally, all famatinite nanoparticles display an EPR signal, indicating trace amounts of paramagnetic Cu(II) present below the detection limit of XPS. For tetrahedrite, EPR signatures were observed only for the Zn-doped and Mn-doped nanoparticles, suggesting signal broadening from Cu–Cu spin exchange or spin–lattice relaxation. This study demonstrates the complementary nature of XPS and EPR techniques for studying the oxidation states of metals in solid-state nanomaterials. Comparing the electronic and magnetic properties of tetrahedrite and famatinite while studying the impact of dopant incorporation will guide future endeavors in designing sustainable, high-performance materials for renewable energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Infrared Nanoimaging of Hydrogenated Perovskite Nickelate Memristive Devices

Solid-state devices made from correlated oxides, such as perovskite nickelates, are promising for neuromorphic computing by mimicking biological synaptic function. However, comprehending dopant action at the nanoscale poses a formidable challenge to understanding the elementary mechanisms involved. Here, we perform operando infrared nanoimaging of hydrogen-doped correlated perovskite, neodymium nickel oxide (H-NdNiO 3 , H-NNO), devices and reveal how an applied field perturbs dopant distribution at the nanoscale. This perturbation leads to stripe phases of varying conductivity perpendicular to the applied field, which define the macroscale electrical characteristics of the devices. Hyperspectral nano-FTIR imaging in conjunction with density functional theory calculations unveils a real-space map of multiple vibrational states of H-NNO associated with OH stretching modes and their dependence on the dopant concentration. Moreover, the localization of excess charges induces an out-of-plane lattice expansion in NNO which was confirmed by in situ X-ray diffraction and creates a strain that acts as a barrier against further diffusion. Our results and the techniques presented here hold great potential for the rapidly growing field of memristors and neuromorphic devices wherein nanoscale ion motion is fundamentally responsible for function.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗