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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 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Modeling Sorption of Water and Vanadium Cations by Ion-Exchange Membranes

We develop a macroscopic model for sorption of ions and solvent by ion-exchange membranes and use it to investigate how different membranes behave when exposed to electrolytes for vanadium flow batteries. The model combines a classical expression for the Gibbs free energy of a moderately concentrated electrolyte containing several ions with a term that describes elastic swelling of a polymer membrane. Parameters describing pairwise interactions between mobile ions and fixed membrane ions were fit to published experimental data and discussed in the context of the competition for sites in ion-exchange membranes. The model provides insights into why sorption of vanadium cations by Nafion is lower than predicted by Donnan theory and why switching to an anion-exchange membrane does not dramatically reduce vanadium sorption.

Electrochemistry↗
DOE OSTI2024

Tailoring Carbide Dispersed Steels: A Path to Increased Strength and Hydrogen Tolerance

The use of transition metal carbides is reported for use as a hydrogen trapping mechanism for ferritic and austenitic steel materials. The program combined computational modeling and simulations to guide experiments towards candidate metal carbide traps, both for interfacial and interior trapping. It was found that interfacial trapping is less effective than interior trapping, with the group IVB transition metal carbides being the most effect internal traps with a loss of carbon. The sub-stoichiometric rocksalt structure accommodate the hydrogen atoms in its octahedral interstices. Using percolation theory, carbon loss of approximately 25% or more was sufficient to ensure an interconnected network of vacancies for such trapping from the surface to the internal sites within the carbide. Using this as a guide, the program developed a means to provide a uniform dispersion of ZrC nanoparticles with either Fe or 304L micron-scale powders which was then consolidated by direct current sintering. Electrolytic hydrogen diffusivity studies confirmed the reduction of hydrogen diffusion in the matrix with increasing ZrC content, which was a linear response over the sample range studied (0.01 to 1.0 wt.%). The consolidated material was micro-tensile tested in either a non-hydrogen or hydrogen charge condition and compared to a control with no carbides. Additions up to 0.05 wt.% ZrC increased the yield strength with no loss in ductility in either the non-hydrogen or hydrogen tested condition. ZrC concentrations above this amount further increased the yield strength at the expense of ductility. While these samples had a lower absolute ductility value prior to failure, the relative change in ductility between the non-hydrogen and hydrogen charge states was less for the carbides than that of the control. Metal-rich ZrC nanoparticles were fabricated through a conformal coating process yielding ZrC0.66 particles that were then incorporated into a metal matrix. Notch fatigue testing in a hydrogen environment was conducted where the number of cycles to failure was found to be less in the control than that of the carbide addition. However, the spread in experimental data and the number of samples tested limits a conclusive outcome based on defects noticed in the gauge section of all the powder processed samples. The collective outcomes of this report provide further insight into the mechanisms by which carbides act as hydrogen traps; a means to process such carbides through powder metallurgy; and their associated mechanical performance in either a non-hydrogen or hydrogen-charged condition.

08 HYDROGEN↗
DOE OSTI2025

Modeling the Behavior of Complex Aqueous Electrolytes Using Machine Learning Interatomic Potentials: The Case of Sodium Sulfate

Understanding the structure and thermodynamics of solvated ions is essential for advancing applications in electrochemistry, water treatment, and energy storage. While ab initio molecular dynamics methods are highly accurate, they are limited by short accessible time and length scales whereas classical force fields struggle with accuracy. Herein, we explore the structure and thermodynamics of complex monovalent-divalent ion pairs using Na 2 SO 4 (aq) as a case study by applying a machine learning interatomic potential (MLIP) trained on density functional theory (DFT) data. Our MLIP-based approach reproduces key bulk properties such as density and radial distribution functions of water. We provide the hydration structure of the sodium and sulfate ions in the 0.1–2 M concentration range and the one-dimensional and two-dimensional potentials of mean force for the sodium–sulfate ion pairing at the low concentration limit (0.1 M), which are inaccessible to DFT. At low concentrations, the sulfate ion is strongly solvated, leading to the stabilization of solvent-separated ion pairs over contact ion pairs. Minimum energy pathway analysis revealed that coordinating two sodium ions with a sulfate ion is a multistep process whereby the sodium ions coordinate to the sulfate ion sequentially. Finally, we demonstrate that MLIPs allow the study of solvated ions beyond simple monovalent pairs with DFT-level accuracy in their low concentration limit (0.1 M) via statistically converged properties from ns-long simulations.

anions↗
DOE OSTI2024

Using data-science approaches to unravel insights for enhanced transport of lithium ions in single-ion conducting polymer electrolyte

Solid polymer electrolytes have yet to achieve the an ionic conductivity > 1 mS/cm at room temperature for realistic applications. This target implies the need to reduce the effective energy barriers of ion transport in polymer electrolytes to around 20 kJ/mol. In this work, we combine information extracted from existing experimental results with theoretical calculations to provide insights into ion transport in single-ion conductors (SICs) with a focus on lithium ion SICs. Through the analysis of temperature-dependent ionic conductivity data obtained from the literature, we evaluate different methods of extracting energy barriers for lithium transport. The traditional Arrhenius fit to the temperature-dependent ionic conductivity data indicates that the Meyer-Neldel rule holds for SICs. However, the values of the fitting parameters remain unphysical. Our modified approach based on recent work (Macromolecules, 56, 15, 6051(2023)), which incorporates a fixed pre-exponential factor, reveals that the energy barriers exhibit temperature dependence over a wide range of temperatures. Using this approach, we identify a series of anions leading to the energy barriers less than 30 kJ/mol, which include trifluoromethane sulfonimide (TFSI), fluoromethane sulfonimide (FSI), and boron-based organic anions. In our efforts to design the next generation of anions, which can exhibit the energy barriers less than 20 kJ/mol, we focused on boron-containing SICs, and performed density functional theory (DFT) based calculations to connect the chemical structures via the binding energy of cation (lithium)-anion pairs with the experimentally derived effective energy barriers for ion transport. Not only have we identified a correlation between the binding energy and the energy barriers, but we also propose a strategy to design new boron-based anions by using the correlation. This combined approach involving experiments and theoretical calculations is capable of facilitating the identification of promising new anions, which can exhibit ionic conductivity $> 1$ mS/cm near room temperature, thereby expediting the development of novel superionic single-ion conducting polymer electrolytes. The published datasets include all the temperature-dependent ionic conductivity collected from the literature with literature DOIs, DFT calculated binding energies, and python scripts to analyze data, construct statistical models, and generate plots.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Using Data-Science Approaches to Unravel Insights for Enhanced Transport of Lithium Ions in Single-Ion Conducting Polymer Electrolytes

Solid polymer electrolytes have yet to achieve the desired ionic conductivity (>1 mS/cm) near room temperature required for many applications. This target implies the need to reduce the effective energy barriers for ion transport in polymer electrolytes to around 20 kJ/mol. In this work, we combine information extracted from existing experimental results with theoretical calculations to provide insights into ion transport in single-ion conductors (SICs) with a focus on lithium ion SICs. Through the analysis of temperature-dependent ionic conductivity data obtained from the literature, we evaluate different methods of extracting energy barriers for lithium transport. The traditional Arrhenius fit to the temperature-dependent ionic conductivity data indicates that the Meyer–Neldel rule holds for SICs. However, the values of the fitting parameters remain unphysical. Our modified approach based on recent work (Macromolecules 2023, 56, 15, 6051), which incorporates a fixed pre-exponential factor, reveals that the energy barriers exhibit temperature dependence over a wide range of temperatures. Using this approach, we identify anions leading to the energy barriers <30 kJ/mol, which include trifluoromethane sulfonimide (TFSI), fluoromethane sulfonimide (FSI), and boron-based organic anions. In our efforts to design the next generation of anions, which can exhibit the energy barriers <20 kJ/mol, we have performed density functional theory (DFT) based calculations to connect the chemical structures of boron-based anions via the binding energy of cation (lithium)-anion pairs with the experimentally derived effective energy barriers for ion hopping. Not only have we identified a correlation between the binding energy and the energy barriers, but we also propose a strategy to design new boron-based anions by using the correlation. This combined approach involving experiments and theoretical calculations is capable of facilitating the identification of promising new anions, which can exhibit ionic conductivity >1 mS/cm near room temperature, thereby expediting the development of novel superionic single-ion conducting polymer electrolytes.

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

Optimization of Magnesium‐Doped Lithium Metal Anode for High Performance Lithium Metal Batteries through Modeling and Experiment

Abstract Lithium (Li)‐magnesium (Mg) alloy with limited Mg amount, which can also be called Mg‐doped Li (Li‐Mg), has been considered as a potential alternative anode for high energy density rechargeable Li metal batteries. However, the optimum doping‐content of Mg in Li‐Mg anode and the mechanism of the improved performance are not well understood. Herein, density functional theory (DFT) calculations are used to investigate the effect of Mg amount in Li‐Mg anode. The Li‐Mg with about 5 wt. % Mg (abbreviated as Li‐Mg5) has the lowest absorption energy of Li, thus all the surface area can be “controlled” by Mg atoms, leading to the smooth and continuous deposition of Li on the surface around the Mg center. A localized high concentration electrolyte enables Li‐Mg5 to exhibit the best cycling stability in Li metal batteries with high‐loading cathode and lean electrolyte under 4.4 V high‐voltage, which is approaching the demand of practical application. This electrolyte also helps generate an inorganic‐rich solid electrolyte interphase, which leads to smooth, compact and less corrosion layer on the Li‐Mg5 surface. Both theoretical simulations and experimental results prove that Li‐Mg5 has optimum Mg content and gives best battery cycling performance.

Gao, Peiyuan↗
DOE OSTI2025

PFSA-Ionomer Adsorption to C and Pt/C Particles in Fuel-Cell Inks

Catalyst inks used to make fuel-cell electrodes consist of Pt/C catalyst particles and a perfluorosulfonic acid (PFSA) ionomer dispersed in water/alcohol solvent mixtures. PFSA ionomer in the ink adsorbs to the surface of the catalyst particles, dictating the dispersion colloid properties. Following adsorption, the subsequent distribution of excess nonadsorbed ionomer in the ink then governs the final structure of the electrode. Here, we characterize the adsorption of the PFSA ionomer onto Pt/C catalyst particles. PFSA adsorption is largely irreversible. Adsorbed sulfonic-acid moieties impart a negative charge on the catalyst surface, causing electrostatic repulsion between the free ionomer in solution and the ionomer-covered Pt/C particle surface. The amount of adsorption is limited by the resulting electrostatic charge that grows as more ionomer adsorbs, and the catalyst surface becomes more negatively charged. Attenuating electrostatic repulsion by increasing the ink ionic strength promotes ionomer adsorption. Electrostatically limited adsorption is observed, irrespective of the solvent water/n-propanol ratio or the catalyst particle porosity and Pt loading. Experimentally measured ionomer adsorption isotherms are well predicted by a Smoluchowski-based kinetic adsorption model, in which the electrostatic energy barrier for adsorption is predicted from DLVO theory. These findings help to unravel the complex phenomena within these colloidal dispersions, allowing for subsequent tailoring of inks to optimize fuel-cell electrode structure and performance.

Adsorption↗
DOE OSTI2023

Vibrational signature of hydrated protons confined in MXene interlayers

Here, the hydration structure of protons has been studied for decades in bulk water and protonated clusters due to its importance but has remained elusive in planar confined environments. Two-dimensional (2D) transition metal carbides known as MXenes show extreme capacitance in protic electrolytes, which has attracted attention in the energy storage field. We report here that discrete vibrational modes related to protons intercalated in the 2D slits between Ti 3 C 2 T x MXene layers can be detected using operando infrared spectroscopy. The origin of these modes, not observed for protons in bulk water, is attributed to protons with reduced coordination number in confinement based on Density Functional Theory calculations. This study therefore demonstrates a useful tool for the characterization of chemical species under 2D confinement.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Yttrium Contenting Compositionally Complex Medium-Entropy Li-Garnet Electrolyte with Improved Ionic Conductivity

The compositionally complex medium/high-entropy design concept can greatly expand the categories and affect the properties of the materials. With such a designing concept, a medium-entropy Li-garnet electrolyte with appropriate yttrium content (formula Li 6.6 La 3 ZrNb 0.3 Ta 0.3 Hf 0.3 Y 0.1 O 12 ) shows a record-high ionic conductivity of ∼5.7 × 10 –4 S/cm, the highest reported for any single-site substituted high/medium-entropy Li-garnet. The assembled Li metal symmetric cells also show stable long-term cycling (0.1 mA/cm 2 for over 200 h). Neutron powder diffraction and Rietveld refinement results indicate that a competing conduction mechanism between (1) occupancy on high mobility of 96h sites and (2) the associated site vacancies and the bond length requires an appropriate content of Y for enhanced ionic conductivity. Li-ion hopping through the bottleneck can also contribute to the conductivity. Finally, density functional theory and Born–Oppenheimer molecular dynamics simulations also indicate the high mobility and number of hopping transitions of Li ions, contributing to the high ionic conductivity.

Li-garnet↗
DOE OSTI2021

Understanding the electron-water interaction at the molecular level: Integrating theory and experiment in the cluster regime

In this final technical report, we summarize our major accomplishments resulting from a combined experimental-theoretical approach that exploits the unique properties of molecular clusters to elucidate how local interactions at the molecular level drive the macroscopic behavior of materials and chemical transformations in liquids. The specific targets for our efforts have need to elucidate how charged entities are accommodated by hydrogen-bonding networks and to establish how the behavior of room temperature ionic liquids can be tailored for specific chemical applications. Because of their central importance in aqueous electrolyte chemistry, we have placed particular emphasis understanding the accommodation of excess electrons and protons by water. These surprisingly complex fundamental electrical charges play a fundamental role in a wide range of chemical and biological processes, and yet even a qualitative picture of their speciation in water and at the air-water interface has proven elusive. The main experimental diagnostic in our approach is to measure and analyze vibrational spectra of temperature and composition controlled molecular aggregates that isolate and amplify the spectral markers for local interactions that are often obscured in measurement on bulk or interfacial water. Our combined experimental-theoretical program has led to a greatly enhanced understanding of the nature of excess electrons and protons in water and in the process developed new and powerful methods of chemical analysis that are currently in use across the chemical sciences.

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

Transport and mechanical behavior in PEO-LLZO composite electrolytes

Abstract Composite solid electrolytes (CEs), wherein ion-conducting polymer and ceramic/glass is mixed, are promising candidates for all-solid-state batteries due to their promise of acceptable ionic conductivity and mechanical properties compared to their individual constituents. While numerous studies have focused on improving the performance of CEs, it is still unclear what the material targets are that can result in improved macroscopic performance especially in light of the coupled needs for high transport and high mechanical strength in these materials. In this study, a two-dimensional (2D) mathematical model is developed to investigate electrochemical and mechanical characteristics of CEs. The model is compared to CEs consisting of poly-ethylene-oxide (PEO) polymer and lithium lanthanum zirconium oxide (LLZO) ceramic material with examination of the impact of varying LLZO volume fractions. The potential drop at the PEO-LLZO interface is evaluated using the junction potential theory. Using experimental data from the literature, the model estimates the ionic conductivity, effective transference number, and mechanical stiffness of the CEs. While the mechanical stiffness improves with increasing volume fraction of LLZO, the impact on conductivity and transference number depends on interfacial resistance at the interface. Finally, the study reports CE’s potential to enhance Li-ion transport and mechanical properties to inhibit lithium (Li) dendrite growth.

25 ENERGY STORAGE↗
DOE OSTI2021

Optimization of Magnesium-Doped Lithium Metal Anode for High Performance Lithium Metal Batteries through Modeling and Experiment

Lithium (Li)-magnesium (Mg) alloy with limited Mg amount, which can also be called Mg-doped Li (Li-Mg), has been considered as a potential alternative anode for high energy density rechargeable Li metal batteries. However, the optimum doping-content of Mg in Li-Mg anode and the mechanism of the improved performance are not well understood. In this study, density functional theory (DFT) calculations are used to investigate the effect of Mg amount in Li-Mg anode. The Li-Mg with about 5 wt. % Mg (abbreviated as Li-Mg5) has the lowest absorption energy of Li, thus all the surface area can be “controlled” by Mg atoms, leading to the smooth and continuous deposition of Li on the surface around the Mg center. A localized high concentration electrolyte enables Li-Mg5 to exhibit the best cycling stability in Li metal batteries with high-loading cathode and lean electrolyte under 4.4 V high-voltage, which is approaching the demand of practical application. This electrolyte also helps generate an inorganic-rich solid electrolyte interphase, which leads to smooth, compact and less corrosion layer on the Li-Mg5 surface. Both theoretical simulations and experimental results prove that Li-Mg5 has optimum Mg content and gives best battery cycling performance.

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

First Principles Determination of the Potential-of-Zero-Charge in an Alumina-Coated Aluminum/Water Interface Model for Corrosion Applications

The surfaces of most metals immersed in aqueous electrolytes have a several-nanometer-thick oxide/hydroxide surface layer. This gives rise to the existence of both metal|oxide and oxide|liquid electrotlyte interfaces, and makes it challenging to correlate atomic length-scale structures with electrochemical properties such the potential-of-zero-charge (PZC). The PZC has been shown to be correlated the onset potential for pitting corrosion. Here, we conduct large-scale Density Functional Theory and ab initio molecular dynamics to calculate the PZC of a Al(111)| γ -Al 2 O 3 (110)| water double-interface model within the context of aluminum corrosion. By partitioning the multiple interfaces involved into binary components with additive contributions to the overall work function and voltage, we predict the PZC to be -1.53 V vs SHE for this model. Furthermore, we calculate the orbital energy levels of defects like oxygen vacancies in the oxide, which are critical parameters in theories associated with pitting corrosion. We predict that the Fermi level at the PZC lies above the impurity defect levels of the oxygen vacancies, which are therefore uncharged at the PZC. From the PZC estimate, we predict the voltage needed to create oxygen vacancies with net positive charges within a flatband approximation.

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

Mechanism of Solid Electrolyte Interphase Formation on Lithium Anodes Studied by Molecular Dynamics Simulations

We investigated the initial formation of the SEI on lithium-metal anodes in presence of several electrolyte compositions using ReaxFF, in absence of a bias potential. We observed the formation of well-defined regions with different density and oxidation states of Li. Dissolution of Li metal atoms results in an uneven distribution of Li in the liquid phase. The electrolyte decomposition mechanism was studied for various electrolyte mixtures. Overall, the reaction mechanisms observed with ReaxFF are in good agreement with previous reports using DFT. However, we found some discrepancies in specific predictions by the ReaxFF that should be addressed in future work.

25 ENERGY STORAGE↗
DOE OSTI2024

Lithium Storage Mechanisms and Electrochemical Behavior of a Molybdenum Disulfide Nanoparticle Anode

This study investigates the electrochemical behavior of molybdenum disulfide (MoS 2 ) as an anode in Li-ion batteries, focusing on the extra capacity phenomenon. Employing advanced characterization methods such as in situ and ex situ X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy, the research unravels the complex structural and chemical evolution of MoS 2 throughout its cycling. A key discovery is the identification of a unique Li intercalation mechanism in MoS 2 , leading to the formation of reversible Li x MoS 2 phases that contribute to the extra capacity of the MoS 2 electrode. Density function theory calculations suggest the potential for overlithiation in MoS 2 , predicting Li 5 MoS 2 as the most energetically favorable phase within the lithiation–delithiation process. Additionally, the formation of a Li-rich phase on the surface of Li 4 MoS 2 is considered energetically advantageous. After the first discharge, the battery system engages in two main reactions. One involves operation as a Li-sulfur battery within the carbonate electrolyte, and the other is the reversible intercalation and deintercalation of Li in Li x MoS 2 . The latter reaction contributes to the extra capacity of the battery. The incorporation of reduced graphene oxide as a conductive additive in MoS 2 electrodes notably improves their rate capability and cycling stability.

Lithium Rich Phase↗
DOE OSTI2025

Elucidating Gas Reduction Effects of Organosilicon Additives in Lithium-Ion Batteries

Lithium-ion batteries (LIBs) with nonaqueous liquid electrolytes are prone to gas generation at elevated voltages and temperatures, degrading battery performance and posing serious safety risks. Organosilicon (OS) additives are an emerging candidate solution for gassing problems in LIBs, but a detailed understanding of their functional mechanisms remains elusive. In this work, we present a combined computational and experimental study to elucidate the gasreducing effects of OS additives. Cell volume measurements and gas chromatography–mass spectrometry reveal that OS additives can substantially reduce gas evolution in LIBs, particularly CO 2 regardless of source. Through density functional theory calculations, we identify multiple plausible pathways for CO 2 evolution, including (1) nucleophile-induced ring-opening of ethylene carbonate (EC) and the subsequent electro-oxidation and (2) direct electro-oxidation of lithium carbonate (Li 2 CO 3 ). Correspondingly, we find that OS additives function via two primary mechanisms: (1) scavenging of nucleophiles such as superoxide (O 2 •– ), peroxide (O 2 2– ), and carbonate ion (CO 3 2– ); (2) oligomerization with ethylene carbonate oxide ion and ethylene dicarbonate ion. Moreover, we discover that OS additives possess strong lithium coordination affinity, which helps further reduce the nucleophilic reaction energies and hence increases their nucleophile-scavenging efficiency. Finally, we provide a mechanistic interpretation for the enhanced gasreduction effects observed with fluorinated OS compounds, corroborated by surface analysis results from X-ray photoelectron spectroscopy. Our study offers the first molecular-level insights into how OS additives contribute to reduced gas formation in LIBs, paving the way for improved safety and performance of LIBs.

25 ENERGY STORAGE↗
DOE OSTI2020

Highly reversible oxygen redox in layered compounds enabled by surface polyanions

Oxygen-anion redox in lithium-rich layered oxides can boost the capacity of lithium-ion battery cathodes. However, the over-oxidation of oxygen at highly charged states aggravates irreversible structure changes and deteriorates cycle performance. Here, we investigate the mechanism of surface degradation caused by oxygen oxidation and the kinetics of surface reconstruction. Considering Li 2 MnO 3 , we show through density functional theory calculations that a high energy orbital (lO 2p’ ) at under-coordinated surface oxygen prefers over-oxidation over bulk oxygen, and that surface oxygen release is then kinetically favored during charging. We use a simple strategy of turning under-coordinated surface oxygen into polyanionic (SO 4 ) 2- , and show that these groups stabilize the surface of Li 2 MnO 3 by depressing gas release and side reactions with the electrolyte. Experimental validation on Li 1.2 Ni 0.2 Mn 0.6 O 2 shows that sulfur deposition enhances stability of the cathode with 99.0% capacity remaining (194 mA h g -1 ) after 100 cycles at 1 C. Our work reveals a promising surface treatment to address the instability of highly charged layered cathode materials.

25 ENERGY STORAGE↗