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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 OSTI2022

The growth and nanothermite reaction of 2Al/3NiO multilayer thin films

Nanothermite NiO–Al is a promising material system for low gas emission heat sources; still, its reactive properties are highly dependent on material processing conditions. In the current study, sputter deposition is used to fabricate highly controlled nanolaminates comprised of alternating NiO and Al layers. Films having an overall stoichiometry of 2Al to 3NiO were produced with different bilayer thicknesses to investigate how ignition and self-sustained, high temperature reactions vary with changes to nanometer-scale periodicity and preheat conditions. Ignition studies were carried out with both hot plate and laser irradiation and compared to slow heating studies in hot-stage x-ray diffraction. Ignition behavior has bilayer thickness and heating rate dependencies. The 2Al/3NiO with λ ≤ 300 nm ignited via solid/solid diffusion mixing (activation energy, E a = 49 ± 3 kJ/mole). Multilayers having λ ≥ 500 nm required a more favorable mixing kinetics of solid/liquid dissolution into molten Al (E a = 30 ± 4 kJ/mole). This solid/liquid dissolution E a is a factor of 5 lower than that of the previously reported powder compacts due to the elimination of a passivating Al oxide layer present on the powder. The reactant mixing mechanism between 300 and 500 nm bilayer thicknesses was dependent on the ignition source's heating rate. The self-propagating reaction velocities of 2Al/3NiO multilayers varied from 0.4 to 2.5 m/s. Pre-heating nanolaminates to temperatures below the onset reaction temperatures associated with forming intermediate nickel aluminides at multilayer interfaces led to increased propagation velocities, whereas pre-heating samples above the onset temperatures inhibited subsequent attempts at laser ignition.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Local and Global Sensitivity Analysis of a Reactive Transport Model Simulating Floodplain Redox Cycling

Reactive transport models (RTMs) are essential tools that simulate the coupling of advective, diffusive, and reactive processes in the subsurface, but their complexity makes them difficult to understand, develop and improve without accompanying statistical analyses. Although global sensitivity analysis (SA) can address these issues, the computational cost associated with most global SA techniques limits their use with RTMs. In this study, we apply distance-based generalized sensitivity analysis (DGSA), a novel and computationally efficient method of global SA, to a floodplain-scale RTM and compare DGSA results to those from local SA. Our test case focuses on the impact of 17 uncertain environmental parameters on spatially and temporally variable redox conditions within a floodplain aquifer. The input parameters considered include flow and diffusion rates, geochemical reaction rates, and the spatial distribution of sediment facies. Sensitivity was evaluated for three distinct components of the model response, encompassing both multidimensional and categorical output. Parameter rankings differ between local SA and DGSA, due to nonlinear effects of individual parameters and interaction effects between parameters. DGSA results show that fluid residence time, which is controlled by aquifer permeability, generally exerts a stronger control on redox conditions than do geochemical reaction rates. Sensitivity indices also demonstrate that sulfate reduction is key for establishing and maintaining reducing conditions throughout the aquifer. Furthermore, these results provide insights into the key drivers of heterogeneous redox processes within floodplain aquifers, as well as the main sources of uncertainty when modeling complex subsurface systems.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Degradation of Poly- and Perfluoroalkyl Substances (PFAS) in Water via High Power, Energy-Efficient Electron Beam Accelerator

The goal of the 2-year workplan was to see if electron beam (EB) could be used to break down a sub-set of the larger chemical family of per and polyfluoroalkylated substances (PFAS) in an energy efficient and economical manner when compared to conventional water treatment technologies. Year one (Y1) work focused on sample EB treatment work in the Fermi National Accelerator Laboratory’s (FNALs) Accelerator Applications Demonstration and Development (A2D2) EB accelerator. While there are reportedly thousands of types of PFAS, for the point of most of the work herein, a small subset was examined, typically perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA). PFOA and PFOS are two of the most well studied PFAS and are studied for baseline evaluations and are considered most useful. The work from Y1 provided information about the optimal operating parameters and additives to use when treating PFOS and PFOA via EB. The data were then used to see where in a water treatment system an EB accelerator would be best suited to treat PFAS. A conventional water treatment technology, GAC, was then compared to e-beam treatment technology with respect to energy and costs for treatment. In year two (Y2), several conventional e-beam accelerator designs, and FNAL’s developmental compact SRF accelerator design, were evaluated for their suitability in PFAS treatment, from an energy efficiency and cost standpoint. Several EB parameters were evaluated and optimized for the removal of PFOA and PFOS from water at normal pressure and temperature, measured as total PFAS removal. Under the optimized test conditions both PFOA showed complete destruction to inorganic fluoride, and PFOS to inorganic fluoride and sulfate, with mass balance. The effect on PFAS removal relative to solution pH, total EB dose, EB dose rate, dissolved oxygen concentration (DO), temperature, and initial PFAS concentration were evaluated. In general, PFOA was easier to destroy than PFOS. Degradation products, typically observed under less-than-optimal EB conditions, provided insight to degradation mechanisms. Products were identified to rule out possible deleterious biproduct formation. The water radiolysis radical reaction kinetics with PFOS and PFOA were not dependent on the initial concentration over 5-orders of magnitude from 2 μg/L to 20 mg/L. This is thought to be because there was an overabundance of the reactive water radiolysis radicals relative to PFAS molecules and largely attributed to aqueous electrons. The reaction rates appeared to be diffusion limited. Testing at higher concentrations (100-200 mg/L) showed a decrease in removal efficiency, suggesting alternative kinetics, possibly second order rates, at higher concentrations. In all, we successfully defined a set of optimal EB parameters to treat PFOA and PFOS at concentrations of 20 mg/L in water with destruction efficiencies near 100%. We further tested the optimized EB parameters with other types of PFAS, including shorter and longer fluorocarbon chain homologs of PFOA and PFOS, and PFAS with alternative functional groups such as sulfonamides. Based on our results EB can be optimized as an effective destructive technology for removing PFAS from water. The conditions optimized for PFOA and PFOS were less effective with ultra-short fluorocarbon compounds like TFMS, PFES, PFPS and PFBS, and likely require re-optimization of parameters to them. In all, it was determined that from a cost and energy efficiency standpoint, EB would be best applied to waste streams with relatively high concentrations of PFOS and PFOA and is not as cost effective as GAC treatment for removing low concentrations of PFAS from water. Higher concentrations of PFAS can be found in the wastewater of conventional treatment processes such as RO and IE and therefore EB may be used to supplement such treatment technologies. Some real-world IE regeneration wash water and RO reject water containing higher concentrations of PFAS and obtained from pilot scale industrial wastewater treatment system at a fluorochemical manufacturing facility, showed that EB could remove PFAS from such types of wastewaters. The IE regenerant wash water appeared to be the most efficient of the two types of wastewaters tested. However, some further optimization of the EB parameters for the specific PFAS types present in those wastewaters may be required. Also, the effects of co-present TOC and mineral salts should be considered during such optimization efforts. From the experimental Y1 results it was seen that the aqueous electron drives degradation of the PFAS. In a hypothetical water treatment skid using EB for PFAS destruction the parameters of the system should be optimized to promote aqueous electron production. Before EB treatment, the PFAS should be preconcentrated when possible, the pH should be raised to pH 10 or higher to enhance aqueous electron production, and the water should be nitrogen purged to remove dissolved oxygen to minimize aqueous electron scavenging. An excel spreadsheet was created that calculates optimal conditions based on inlet PFAS concentration and desired outlet concentration, by optimizing the accelerator power, dose rate, water treatment rate, pH and dissolved oxygen levels to reach the desired endpoint. Given this information on accelerator operating conditions five different EB accelerator systems were compared. One EB system was a continuous-wave, linear superconducting accelerator being designed at Fermilab. Three other EB systems (IMPELA at 5% and 25% duty factor and the ILU-14) were normal conducting pulsed linear accelerators. The fifth system was an IBA Rhodotron which is a normal conducting, circular, continuous-wave accelerator. The accelerator efficiency (% of the incoming power that is used in water treatment) was the dominating factor in accelerator choice. The radio frequency (RF) power supply and the accelerator design (superconducting versus warm technology) drive the accelerator efficiency. The IBA Rhodotron was seen to be the most energy efficient commercially available technology with a wall-plug (total) power efficiency of 43% at 400 kW. The Fermilab design, with a prototype for a different application currently being fabricated, was the most energy efficient at 55% when driven by a Klystron RF power supply and as high as 77% when powered by a magnetron. As the Fermilab design was the most energy efficient by approximately 10-30%, further design work was done on the accelerator and beam delivery system specific to the destruction of PFAS in water. The Fermilab design is unique from industrial accelerators in that is superconducting. Superconducting technology allows for the acceleration of electrons without losses. The accelerator must be cooled to below the point where it is superconducting and is operated around 4 degrees Kelvin. The bulk of the design work for the accelerator is on making the accelerator as energy efficient as possible so that it does not require liquid helium and can be cooled with conduction cooling via cryocoolers. Final design work resulted in an EB accelerator that would operate at minimally 200 kW and 10 MeV. Prototype construction would cost $\$ $7.8 million dollars when driven by a Klystron power supply. A second version of the same accelerator would cost $\$ $5.5 million dollars when driven by a magnetron that is still under development. The commercially available 300 kW IBA Rhodotron cost was estimated at approximately $\$ $9 million. While it is hard to directly compare, an operational GAC system used by 3M for groundwater treatment capital cost (2022 dollars) was estimated to cost $\$ $3.3 million. While the capital expense of the EB accelerator systems was higher than GAC, the accelerator EB treatment would result in destruction of the PFAS and not just sequestration of PFAS to form a new waste stream that requires further treatment or disposal. The operating cost to destroy the PFAS via 400 kw EB system was less than $\$ $1000/kg of PFAS destroyed when treating at a 20 mg/L PFAS concentration, compared to GAC with operating costs that calculated at $\$ $27,530 per kg of PFAS sequestered when treating 100 μg/L PFOA and PFOS combined concentration.

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

Mechanisms of mechanochemical synthesis of cesium lead halides: pathways toward stabilization of α-CsPbI 3

Cesium lead iodide with cubic perovskite structure (α-CsPbI 3 ) is gaining significant interest in photovoltaic applications due to its excellent absorbance of the visible solar light and other attractive optoelectronic properties. However, the synthesis of stable α-CsPbI 3 poses a significant challenge. Mechanochemical synthesis is emerging as a suitable method for the preparation of cesium lead halides. This work investigates the ball milling-induced synthesis of cesium lead halides perovskite phase using halide mixing or doping approaches. The synthesis in the CsI + PbI 2 , CsBr + PbBr 2 , CsBr + PbI 2 , and CsI + PbI 2 + NdI 3 mixtures and halide exchange reactions in the CsPbBr 3 + 3KI and CsBr + PbBr 2 + 3KI systems are investigated to elucidate the mechanism of this process. Then, CsPb(I 1–x Br x ) 3 and CsPb( 1–y )Nd y I 3 materials with different x and y ratios are prepared, and their stability is probed in the air using light absorption spectroscopy. These results suggest that Nd doping is more efficient in the stabilization of the perovskite structure than partial replacement of iodine with bromine. Microstructure observations reveal the existence of two different product formation mechanisms depending on the mechanical properties of reactants. The results reveal that the milling temperature has a significant impact on the reaction kinetics. Here, the produced particles nucleate and grow at the reactant interface and retard the synthesis reaction by creating a diffusion barrier. Extended milling reduces the product particle size and creates fresh contact between reactants, thus facilitating reaction completion.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Using Homogenized Models to Explore the Effect of Fracture Densities on Weathering

Despite its importance, only a few researchers have incorporated the effects of fracturing into models of reactive transport for rock weathering. Here we explore 2D simulations that describe weathering under conditions of diffusive and advective transport within heterogeneous media consisting of rocky blocks and fractures. In our simulations, the Darcy velocities vary in space and time and depend on weathering processes within the rock matrix. We explore simulations with saturated and unsaturated flow for weathering bedrock that consists of blocks separated by inert or weathered material. The simulations show that a simplified homogenized model can approximate exact solutions for some of the simulated columns and hills and can allow exploration of coupling between flow and reaction in fractured rock. These hillslope simulations document that, even in the presence of 2D water flow, i) an increase in fracture density results in faster weathering advance rates; and ii) the water table locates deeper for a rock system that is weathered and fractured rather than weathered and unfractured. Some of these patterns have also been observed for natural systems. But these simulations also highlight how simplified models that do not use appropriate averaging of heterogeneities can be inaccurate in predicting weathering rate for natural systems. For example, if water flows both vertically and laterally through the vadose zone of a hill, then a prediction of the depth of regolith that is based on modeling strictly unidirectional downward infiltration will be unrealistically large. Likewise, if the fracture density observed near the land surface is used in a model to predict depth of weathering for a system where the fracture density decreases downward, the model will overestimate regolith depth. Learning how to develop accurately homogenized models could thus enable better conceptual models and predictions of weathering advance in natural systems.

58 GEOSCIENCES↗
DOE OSTI2021

Harnessing autocatalytic reactions in polymerization and depolymerization

Abstract Autocatalysis and its relevance to various polymeric systems are discussed by taking inspiration from biology. A number of research directions related to synthesis, characterization, and multi-scale modeling are discussed in order to harness autocatalytic reactions in a useful manner for different applications ranging from chemical upcycling of polymers (depolymerization and reconstruction after depolymerization), self-generating micelles and vesicles, and polymer membranes. Overall, a concerted effort involving in situ experiments, multi-scale modeling, and machine learning algorithms is proposed to understand the mechanisms of physical and chemical autocatalysis. It is argued that a control of the autocatalytic behavior in polymeric systems can revolutionize areas such as kinetic control of the self-assembly of polymeric materials, synthesis of self-healing and self-immolative polymers, as next generation of materials for a sustainable circular economy. Graphic Abstract

36 MATERIALS SCIENCE↗
DOE OSTI2023

Machine learning-based ethylene and carbon monoxide estimation, real-time optimization, and multivariable feedback control of an experimental electrochemical reactor

Electrochemical reduction of CO 2 gas is a novel CO 2 utilization technique that has the potential to mitigate the global climate crisis caused by anthropogenic CO 2 emissions, and enable the large-scale storage of energy generated from renewable sources in the form of carbon-based chemicals and fuels. However, due to the complexity of the electrochemical reactions, the explicit first-principles models for CO2 reduction are not available yet, and there has been a limited effort to develop process modeling, optimization and control of CO 2 electrochemical reactors. To this end, a rotating cylinder electrode (RCE) reactor has been constructed at UCLA to understand the mass transfer and reaction kinetics effects separately on the productivity. In the RCE reactor, the applied potential strongly influences the reaction energetics and the electrode rotation speed affects the hydrodynamic boundary layer and modifies the film mass transfer coefficient, which involves convective and diffusive transport. Further, the present work aims to develop a multi-input multi-output (MIMO) control scheme for the RCE reactor that integrates techniques from artificial and recurrent neural network modeling, nonlinear optimization, and process controller design. Specifically, production rates of two products from the experimental reactor, ethylene and carbon monoxide, are controlled by manipulating two inputs, applied potential and catalyst rotation speed. Process dynamics and controllability are analyzed, a feedback control strategy is designed and the controllers are tuned accordingly. The experimental electrochemical cell is employed to gather data for process modeling and implement the multivariable control system. Finally, the experimental results are presented which demonstrate excellent closed-loop performance by the control system and regulation of the outputs at three different set-points including an economically-optimal set-point.

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

The São Paulo Potential and the 3 He Breakup Reaction at 130 MeV on 93 Nb and 197 Au

Nuclear reactions induced by weakly bound nuclei often result in the emission of light particles as products of the projectile breakup. The incident particle is expected to fragment before reaching the interior of the target nuclei, a characteristic that tends to favor forward angular emission. Although the first models developed for such reactions were proposed many decades ago by Udagawa and Tamura, Ichimura, Austern, Vincent, and Kasano, and Hussein and McVoy, to this date most of the attention has been dedicated to the breakup of the deuteron and other very weakly bound systems, while more strongly bound projectiles have not been fully explored. Here, we describe the production of protons and deuterons from the breakup of 3He. The breakup of 3 He on two heavy targets, 93 Nb and 197 Au, is analyzed in this study. However, the incoming energy involved is much larger than that of the standard phenomenological optical potentials available in the literature for the 3He entrance channel. We have overcome this difficulty by using the São Paulo potential and adjusting the nuclear diffusivity. The deuteron inclusive spectra were calculated at several angles and compared well with the experimental data. Theoretical proton emission predictions are also given for future reference, since no inclusive measurements were performed for the targets under study. Finally, one of our goals is to verify the description of deuteron emission from fast projectiles, for which many partial waves contribute to the scattering process.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Real-Time Detection of Hydrogen and Ammonia Isotopologues for Impurity Removal and Recovery of Tritium

To accommodate gas measurements for impurity removal and recovery of tritium, a silver-coated optical or waveguide is employed for collecting Raman scattered signals to determine relative hydrogen and ammonia isotopologue populations in real time. The data and results presented here demonstrate an analytical methodology for the analysis of four ammonia and three hydrogen isotopologues in a hydrogen–deuterium exchange reaction by gas phase Raman spectroscopy. Standard chemometric modeling techniques effectively unravel the signatures of the isotopologues involved observed here; however, a sophisticated quantum chemical approach supports the spectral assignments. An interpretation of the data presented here can emphasize the practicality and reliability of the gaseous monitoring system in complex chemical environments for the hydrogen fuel economy as well as the more distant energy source from a facility that handles tritium. There are still considerable concerns about the measurement of tritium in isotope separation and radiological impurities from gas processing. A common impurity in gas processing is ammonia, which can form readily in the presence of nitrogen and tritium. Substituted ammonia (NQ 3 ), where Q = H, D, or T, is traditionally removed through getters or diffusers along with other non-hydrogen contaminants. A preferable analytical approach is noninvasive and can be deployed for real-time process evaluation in radiological environments.

Ammonia↗
DOE OSTI2020

Intercalation of Mg into a Few-Layer Phyllomanganate in Non-aqueous Electrolytes at Room Temperature

The use of oxide cathodes in Mg batteries would unlock a potential energy storage system that delivers high-energy density. However, poor kinetics of Mg diffusion in known solid oxide lattices strongly limits reversible intercalation, which motivates the sustained exploration of new candidates. Herein, nanocrystals of a few-layer phyllomanganate, reminiscent of the mineral vernadite, were shown to have considerable electrochemical activity toward Mg intercalation at room temperature, where it delivered similar to 190 mAh g- 1 at similar to 1.9 V (vs Mg/Mg 2+ ) in batteries paired with a Mg metal anode. Multimodal characterization confirmed the notable degree of reversible intercalation by probing the structural, compositional, and redox changes undertaken by the oxide. Distinct levels of Mg activity were also observed while varying the content of small amounts of lattice water and the temperature of the reaction. The results reaffirm the prospects for operational Mg batteries using oxide cathode in moderate conditions, overcoming current limits of performance of this prospective technology.

25 ENERGY STORAGE↗
DOE OSTI2020

Flue Gas CO 2 Capture via Electrochemically Mediated Amine Regeneration: Desorption Unit Design and Analysis

We analyzed the performance of an electrochemical desorption unit to be implemented in an electrochemically mediated amine regeneration (EMAR) process, which separates CO 2 and regenerates the amine upon modulation of a targeted species that complexes with the amine molecules. Using a simplified one-dimensional boundary layer model, we combined the kinetic expressions of the faradaic reactions with mass transfer effects to analyze the polarization behavior of the flow cell. Mass transfer limitations become dominant at high current densities, leading to increases in energy consumption. An understanding of scaling laws with key parameters, such as the Sherwood number, is required to achieve high power operation with minimal mass transfer losses. Because the EMAR chemistry is sensitive to temperature, heat distribution in the unit is also examined. Our results indicate that the desorption performance increases with addition of a high-temperature heat source. Additionally, incorporation of membrane crossover suggests energy losses because of diffusion and migration of active species. Furthermore, these findings inform on scaling laws for at-scale desorber design and provide a model for scaling up the EMAR system for larger scale operations.

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

All-Atom Molecular Dynamics Simulations of the Temperature Response of Densely Grafted Polyelectrolyte Brushes

Water acts a “good” solvent for most polyelectrolyte (PE) systems due to its high dielectric strength. Theoretical and experimental studies have highlighted some remarkably unconventional properties of strongly water-swollen PE brushes such as a reduction in brush height with increase in temperature. However, an understanding of the atomistic-scale response of the grafted PE chains as well as the local arrangement and organization of the brush-supported counterions and water molecules to changes in temperature is missing. Here, we conduct an all-atom molecular dynamics (MD) study to probe the influence of temperature on the “microstructure” of densely grafted, fully ionized polyacrylic acid (PAA) brushes. The atomistic insights obtained from our study shed light on prior experimental observations and elucidate the key role played by changes in hydrogen bonding network in dictating the hydrophilicity of the brushes. In addition to the temperature-mediated reduction in height of the PE brush layer, we study the influence of temperature on several properties of the brush-supported water molecules such as the number distribution and kinetics of water-water and water-PE hydrogen bonds (HBs), mass density, orientational tetrahedral order parameter, and the activation energy associated with the self-diffusion of water. The effect of temperature on the properties of the brush-trapped counterions is also quantified via changes in their solvation structure, counterion-water radial distribution function (RDF), and the translational mobility. Our findings unravel several hitherto unknown phenomena such as the enhanced propensity for attaining PE brush-induced “water-in-salt”-like scenarios at elevated temperatures, and an increase in the activation energy for the self-diffusion of water with increase in the degree of PE brush-induced nanoconfinement (from ‘bulk water’ to ‘sparsely grafted PE brushes’ to ‘densely grafted PE brushes’). Further, we anticipate that this work will be helpful in improving our predictive capabilities of the temperature response of water-swollen PE brushes, which would be instrumental for better design of several PE brush systems used in a multitude of applications.

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

Visualizing degradation mechanisms in a gas-fed CO 2 reduction cell via operando X-ray tomography

We utilize operando X-ray computed tomography, coupled with real-time electrochemical analysis, to reveal the underlying failure mechanisms of membrane electrode assemblies (MEAs) for electrochemical CO 2 reduction (eCO 2 R). Through operando imaging, we can obtain unprecedented insights into the dynamic behavior of the MEA under different operating conditions, revealing critical changes in interface interactions, phase distribution, and structural integrity over time. Our findings identify phenomena giving rise to the transition from CO 2 R to the hydrogen evolution reaction (HER), as evidenced by shifts in cathode potential and CO 2 R selectivity. The formation of inhomogeneous precipitates at the gas diffusion electrode disrupts the CO 2 supply and reduces the active sites for eCO 2 R, resulting in a shift toward H2 production during low current density operation. Additionally, under high current density conditions, rapid water crossover up to the microporous layer/gas diffusion layer promotes the transition from CO 2 R to HER, further shifting cell potential toward anodic direction. Oscillating voltage conditions reveal the dissolution and regrowth of precipitates, providing direct visualization of the competing selectivity of CO 2 R and HER. This work offers new insight into the degradation mechanisms of MEAs, with implications for the design of more durable CO 2 R systems.

Lee, Sol A [California Institute of Technology (Ca↗
DOE OSTI2022

Spontaneous Lithiation of Binary Oxides during Epitaxial Growth on LiCoO 2

Epitaxial growth is a powerful tool for synthesizing heterostructures and integrating multiple functionalities. Interfacial mixing can readily occur at temperatures required for complete film crystallization and can significantly modify the properties of layered structures, particularly for those containing energy storage materials with smaller cations. Here we show a two-step sequence involving the growth of an epitaxial LiCoO 2 cathode layer followed by the deposition of a binary transition metal oxide (WO 3 , TiO 2 , and others) in which controlled lithiation of the binary oxide occurs. Orientation-controlled epitaxial synthesis of the model solid-state-electrolyte Li 2 WO 4 and model anode material Li 4 Ti 5 O 12 occurs as WO 3 and TiO 2 nucleate their respective host lattices and attract Li ions from the underlying cathode. The cathode layer readily provides a tunable amount of Li ions for the controlled lithiation of the subsequent layer. We demonstrate that this approach can be used for energy materials discovery and exploring different combinations of epitaxial interfaces that can serve as well-defined model systems for mechanistic studies of energy storage and conversion processes.

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

Phase field-volumetric lattice Boltzmann model of ion uptake in porous nuclear waste form materials under continuous flow

The flow field within the mesopores of sorbent particles plays a crucial role in radionuclide diffusion and ion uptake kinetics, thus, impacting the overall performance of porous nuclear waste form materials. To fundamentally understand the influence of microstructures and material properties on the radionuclide absorption and retention processes requires a coupled multi-physics model that considers the advection and diffusion within the flow field, the reaction at liquid-solid interfaces, and finally, the solid-state diffusion within a complex nanoporous medium. Here, this study employs the volumetric lattice Boltzmann method (VLBM) to accurately and efficiently calculate the steady state velocity field inside the mesopores of sorbent particles. The obtained velocity field is then utilized to calculate the advection of ions in the steady flow. A phase field (PF) model of ion uptake is used to describe the reaction occurring at the solid-liquid interface and diffusion inside the porous medium. The integrated PF-VLBM model is verified in terms of the mass conservation and numerical efficiency and validated qualitatively with experimental observation data. Then, it is applied to study the influence of thermodynamic and kinetic properties, as well as flow field conditions on the ion uptake kinetics. The numerical results demonstrate that the ion uptake kinetics in porous particles has three distinct stages, which is in agreement with the observations in continuous flow experiments. In the first stage, the kinetics is predominantly controlled by the flow field and ion diffusivity in the liquid phase. The kinetics in the second stage is primarily governed by ion diffusivity in the solid phase. In the third stage the system reaches a dynamic equilibrium with a net zero uptake flux at the interface. It is also found that porous structures significantly affect the efficiency and capacity of ion uptake. The simulation results can help to understand the physics behind the observed ion uptake kinetics in experiments and to facilitate the development of constitutive equations that can account for heterogeneous microstructures in engineering performance codes.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Quantitative local state of charge mapping by operando electrochemical fluorescence microscopy in porous electrodes

We introduce operando quantitative electrochemical fluorescence state of charge mapping (QEFSM), a non-invasive technique to study operating electrochemical systems along with a new design of optically transparent microfluidic redox flow cells compatible with the most demanding optical requirements. QEFSM allows quantitative mappings of the concentration of a particular oxidation state of a redox-active species within a porous electrode during its operation. In this study, we used confocal microscopy to map the fluorescence signal of the reduced form of 2,7-anthraquinone disulfonate (AQDS) in a set of multistep-chronoamperometry experiments. Calibrating these images and incorporating an analytical model of quinhydrone heterodimer formation with no free parameters, and accounting for the emission of each species involved, we determined the local molecular concentration and the state of charge (SOC) fields within a commercial porous electrode during operation. With this method, electrochemical conversion and species advection, reaction and diffusion can be monitored at heretofore unprecedented transverse and axial resolution (1 μm and 25 μm, respectively) at frame rates of 0.5 Hz, opening new routes to understanding local electrochemical processes in porous electrodes. Here, we observed pore-scale SOC inhomogeneities appearing when the fraction of electroactive species converted in a single pass through the electrode becomes large.

42 ENGINEERING↗
DOE OSTI2025

In Situ Neutron Reflectometry Reveals the Interfacial Microenvironment Driving Electrochemical Ammonia Synthesis

Electrified interfaces are critical to the performance of energy systems and often demonstrate substantial complexity under operating conditions. A nanoscale understanding of the interfacial microenvironment, i.e., the solid-electrolyte interphase (SEI), in lithium-mediated nitrogen reduction (Li–N 2 R) is key for realizing efficient ammonia (NH 3 ) production. Herein, we used time-resolved neutron reflectometry (NR) to observe SEI formation under Li–N 2 R conditions. We found that the LiBF 4 -based electrolyte provided a substantially more well-defined SEI layer than previous SEI NR interrogations that used LiClO 4 , highlighting the underlying chemistry that dictates electrolyte design and enabling new NR-based studies. Using in situ NR, we found that the LiBF 4 -derived SEI under Li–N 2 R conditions comprises a thick, diffuse outer layer and a thin, compact inner layer at low current cycling (<2 mA/cm 2 ), revealing a structure which ex situ studies have not been able to probe. Increased current cycling and sustained current cycling led to the merging of the layers into a single-layer SEI. Here, we used isotope contrast methods with d 6 -EtOH and d 8 -THF to drive time-resolved tracking of SEI growth at low current cycling, revealing that the proton donor modifies the inner layer, and the solvent modifies the outer layer. Li dendritic growth was observed in the absence of a proton donor. Neutron absorption also indicated the presence of boron in the SEI, underscoring the value of neutron-based interrogation. Our results inform Li-based systems and reaction microenvironments, and these methods can be applied broadly to interfacial energy technologies.

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

Impact of Concurrent Solubilization and Fines Migration on Fracture Aperture Growth in Shales during Acidized Brine Injection

Acidic hydraulic fracturing fluid chemically and physically alters shale rock fabric during injection and shut-in, creating a “reaction-altered zone” along the fracture faces. To better characterize the variable thickness and composition of this reaction-altered zone under advective flow, we take a coupled experimental and modeling approach. A fluidic cell, with six fiducial markers, is first fabricated to keep the rock sample in place during the core floods and to allow image alignment of acquired images. Then, we conduct a series of reactive core floods in a clay-rich siliceous Wolfcamp shale sample with 10 wt % carbonate, using a synthetic fracturing fluid under no confining stress and at room temperature. High-resolution computed tomography (CT) scans are periodically conducted to observe the spatial alteration of the fracture network. We then perform scanning electron microscopy (SEM-EDS) on the two orthogonal surfaces (fracture surface and freshly cut profile face) to generate high-resolution elemental maps that show the change in mineralogy, both with distance along a given flow path along a fracture surface and with depth from the fracture surface into the shale matrix. These results are contrasted against a two-dimensional (2D) advection-diffusion reaction model developed previously for batch reactions between shale and synthetic fracturing fluids. The model simulates the geochemical interaction occurring at the fracture/matrix interface and penetrating into the shale matrix during the reactive core flood. Both model and experimental results show that the acidic brine is neutralized during the core flood, corresponding to an increase in fracture aperture as a function of fluid volume injected with the greatest change near the inlet. SEM-EDS scans reveal significant dissolution of carbonates on the fracture surface without pyrite oxidation. The reactive transport model indicates that carbonate depletion into the shale interior should be observable, yet SEM-EDS shows no discernible loss of carbonate in the orthogonal profile face. The combination of these observations suggests an additional fracture evolution mechanism in the reactive system, i.e., fines migration. We show that fines migration enhances the access of fracturing fluid to the matrix resulting in a more pronounced fracture widening. Finally, we conclude that coupled mineral dissolution and fines migration govern fracture aperture growth during acidized brine injection. In this work, we effectively show the underlying risk of relying solely on models that do not include an important (transport) process that can alter the system significantly and propose a combined chemomechanical mechanism for fracture evolution appropriate for this shale mineralogy.

58 GEOSCIENCES↗