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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 1,171 records · Page 65
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Macroscale Control of Reactivity using 3D Printed Materials with Intrinsic Catalytic Properties

The morphology of heterogeneous catalysts can impact their performance. However, standard manufacturing methods like extrusion or pelleting offer little options for tailoring catalyst shape. Herein, stereolithographic 3D printing is used to produce catalysts with controlled topologies to enhance their performance. A series of magnetic stir-bar compartments (SBC) were 3D printed and tested as catalysts for sucrose hydrolysis. The SBC were printed using acrylic acid (AA) and 1,6-hexanediol diacrylate (HDDA) as acid sites and hydrophobic crosslinking domains, respectively. Variations in the number and tilt direction of the SBC blades produced significant changes in their apparent catalytic activities. These changes resulted from differences in the fraction of active surface effectively interacting with the reactants in solution, as revealed by computational fluid dynamics simulations. Moreover, varying HDDA:AA ratios in SBC regulated reactant-surface interactions to control catalytic activity. Overall, 3D printing catalysts enables quick performance optimization by simultaneously controlling macroscopic structure and molecular composition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Electrochemical reactivity of atomic and molecular species under solid-state confinement

The nanoconfinement of electrochemically-active guest species in host solid state electrode materials provides opportunities to tune mass transport between the bulk electrolyte and inner surface of the electrode, enhance electron-transfer rates, and/or improve the stability and dispersion of active material. Here, this review summarizes recent experimental and theoretical electrochemical studies of three types of nanoconfined guest species: (1) ion adsorption of electrolyte ions, (2) confined redox-active molecules, and (3) electrocatalytic reactions of confined ions/solvents and catalytic particles. The examples discussed in this review illustrate how the confinement of guest species within enclosed spaces with nanoscale dimensions – such as pores, pockets, channels, and interlayers – can lead to improved electrochemical performance.

25 ENERGY STORAGE↗
DOE OSTI2020

Reactive chemical transport simulations of geologic carbon sequestration: Methods and applications

Chemical reaction simulations are considerably used to quantitatively assess the long-term geologic carbon sequestration (GCS), such as CO 2 sequestration capacity estimations, leakage pathway analyses, enhanced oil recovery (EOR) efficiency studies, and risk assessments of sealing formations (caprocks), wellbores, and overlying underground water resources. All these require a deep understanding of the CO 2 - associated chemical reactions. To ensure long-term, safe CO 2 sequestration in the intended formations, modeling is the only way to plausibly assess the CO 2 flow, reaction, and transport over thousands of years. This review summarizes the multiple methodologies for describing homogeneous and heterogeneous chemical reaction patterns and multiscale application examples, the recent progress and current status of chemical reaction simulations for GCS, and the impact of such simulations on geological CO2 sequestration performance. Technical gaps and future challenges are also discussed for further study. The trends and challenges of such studies include: (1) the combination of coupled chemical, mechanical, and transport processes with calibrated experiments and associated uncertainty/risk assessments; (2) enhancement of the ability to simulate detailed geophysical and geochemical equations to mimic in situ conditions; and (3) characterization of multiscale subsurface systems with detailed conceptual models and assignment of suitable boundary conditions for field-scale sequestration fields. One major gap remaining is the current lack of accurate (and scale-justified) kinetic and equilibrium chemical reaction parameters under reservoir conditions. Advanced models that couple chemical, mechanical, and transport processes with scale-justified parameters, from lab to field-scale experiments, are required for quantitative assessments of sequestration capacity and the long-term safety of GCS projects.

58 GEOSCIENCES↗
DOE OSTI2022

Plutonium reactive transport in fractured granite: Multi-species experiments and simulations

Plutonium (Pu) in the subsurface environment can transport in different oxidation states as an aqueous solute or as colloidal particles. The transport behavior of Pu is affected by the relative abundances of these species and can be difficult to predict when they simultaneously exist. This study investigates the concurrent transport of Pu intrinsic colloids, Pu(IV) (aq) and Pu(V-VI) (aq) through a combination of controlled experiments and semi-analytical dual-porosity transport modeling. Pu transport experiments were conducted in a fractured granite at high and low flow rates to elucidate sorption processes and their scaling behavior. In the experiments, Pu(IV) (aq) was the least mobile of the Pu species, Pu(V-VI) (aq) had intermediate mobility, and the colloidal Pu, which consisted mainly of precipitated and/or hydrolyzed Pu(IV), was the most mobile. The semi-analytical modeling revealed that the sorption of each Pu species was rate-limited, as the sorption could not be described by assuming local equilibrium in the experiments. The model was able to describe the sorption of the different Pu species that occurring either on fracture surfaces, in the pores of the rock matrix, or simultaneously in both locations. While equally good fits to the data could be achieved using any of these assumptions, a fracture-dominated process was considered to be the most plausible because it provided the most reasonable estimates of sorption rate constants. Importantly, a key result of this work is that the sorption rate constant of all Pu species tends to decrease with increasing time scales, which implies that Pu will tend to be more mobile at longer time scales than observations at shorter time scales suggest. This result has important implications for predicting the environmental impacts of Pu in the safety assessments of geologic repositories for radioactive waste disposal, and we explore potential mechanistic bases for upscaling the sorption rate constants to time and distance scales that cannot be practically evaluated in experiments.

58 GEOSCIENCES↗
DOE OSTI2024

Electrolyte Design for Silicon-Based Li-Ion Battery Guided by Chemical Reactivity of Solvents with a Model Silicon Anode

Here, the use of a model compound trimethylsilyllithium was demonstrated to study the chemical reactions of electrolyte with as a principal guide to design electrolyte for silicon-based Li-ion battery. Me 3 Si - anion initiates ring-opening polymerization of EC leading to the formation of poly(ethylene ether carbonate), which subsequently defragments into oligomers and dissolves in electrolyte. FEC was found to react differently, generating LiF and vinylene carbonate (VC). Further reaction of VC with Me 3 SiLi generated poly(hydroxymethylene), which is a nonsoluble polymer and the critical SEI component. The insights from this study have guided the new electrolyte design for the Si-based battery.

25 ENERGY STORAGE↗
DOE OSTI2020

Electrochemical Reactivity and Passivation of Silicon Thin-Film Electrodes in Organic Carbonate Electrolytes

This work focuses on the mechanisms of interfacial processes at the surface of amorphous silicon thin-film electrodes in organic carbonate electrolytes to unveil the origins of the inherent nonpassivating behavior of silicon anodes in Li-ion batteries. Attenuated total reflection Fourier-transform infrared spectroscopy, X-ray absorption spectroscopy, and infrared near-field scanning optical microscopy were used to investigate the formation, evolution, and chemical composition of the surface layer formed on Si upon cycling. Herein, we found that the chemical composition and thickness of the solid/electrolyte interphase (SEI) layer continuously change during the charging/discharging cycles. This SEI layer “breathing” effect is directly related to the formation of lithium ethylene dicarbonate (LiEDC) and LiPF6 salt decomposition products during silicon lithiation and their subsequent disappearance upon delithiation. Furthermore, the detected appearance and disappearance of LiEDC and LiPF6 decomposition compounds in the SEI layer are directly linked with the observed interfacial instability and poor passivating behavior of the silicon anode.

25 ENERGY STORAGE↗