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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Subcontract Report: Diffusion Mechanisms and Bond Dynamics in Solid Electrolyte Ion-Conductors

We employ first-principles molecular dynamics simulations and Maximally Localized Wannier Function (MLWF) analysis to explore how halide substitution and nano-phase microstructures affect diffusivity, through the activation energy barrier - E a and D 0 , in the solid electrolyte Li 3 InBr 6-x Cl x . We find that nano-phase microstructures with x=3 (50-50 Br-Cl) mixed composition have a higher diffusivity compared to x=2 and x=3 solid solutions. There is a positive linear relationship between ln(D 0 .) and E a , which suggests that for superionic conductivity optimizing both the activation energy and the D 0 is important. Bond frustration due to mismatch in crystal geometry and ideal coordination number leads to especially high diffusivity through a high D 0 in the x=3 composition.

25 ENERGY STORAGE↗
DOE OSTI2018

Solid electrolytes for solid-state and lithium-sulfur batteries

The stringent demands placed on batteries by emerging vehicle technologies such as plug-in and battery electric vehicles suggest that improvements in the safety and performance of electrochemical energy storage devices, as well as concurrent reductions in their cost, are highly desirable. Current strategies for improving performance have largely focused on Li-ion battery chemistries. In this project went beyond the state of the art by pursuing electrolyte chemistries that will enable the use of Li metal anodes and sulfur cathodes, either concurrently in a solid state Li-S battery, or as a means to achieve a Li metal anode which is stable upon cycling. More specifically, our effort advanced strategies to enable Li metal anodes for myriad beyond Li-ion chemistries . LLZO garnet (Li 7 La 3 Zr 2 O 12 ) is the first bulk-scale ceramic electrolyte to exhibit the combination of superionic conductivity (1mS/cm at 298K), high shear modulus (61 GPa) to suppress Li dendrite penetration, and apparent electrochemical stability (0-6V vs Li/Li + ), thus enabling Li metal anodes. However, to date there are no reports confirming LLZO can tolerate current densities > 1mA/cm 2 , thus demonstrating relevance to PHEV/EV batteries. Our goal was to investigate the mechanisms that govern the Li-LLZO interfacial stability as a function of current density. We determined that defects in polycrystalline LLZO reduce the critical current density (CCD). Primarily contaminants on the LLZO surface and grain boundaries were the primary defects the limited the CCD. Using our experience with synthesis and processing (Sakamoto and Wolfenstine) and sophisticated materials characterization (Nanda), we precisely controlled atomistic and microstructural defects and correlated their effects on controlling the critical current density. These data fed into multi-scale computation models (Siegel and Monroe) to isolate and quantify the roles that each defect played in controlling the critical current density. Bridging this knowledge gap allowed us to demonstrate that LLZO can withstand > 1mA/cm 2 .

25 ENERGY STORAGE↗
DOE OSTI2023

Thermal Polymorphism in CsCB11H12

Thermal polymorphism in the alkali-metal salts incorporating the icosohedral monocarba-hydridoborate anion, CB11H12−, results in intriguing dynamical properties leading to superionic conductivity for the lightest alkali-metal analogues, LiCB11H12 and NaCB11H12. As such, these two have been the focus of most recent CB11H12− related studies, with less attention paid to the heavier alkali-metal salts, such as CsCB11H12. Nonetheless, it is of fundamental importance to compare the nature of the structural arrangements and interactions across the entire alkali-metal series. Thermal polymorphism in CsCB11H12 was investigated using a combination of techniques: X-ray powder diffraction; differential scanning calorimetry; Raman, infrared, and neutron spectroscopies; and ab initio calculations. The unexpected temperature-dependent structural behavior of anhydrous CsCB11H12 can be potentially justified assuming the existence of two polymorphs with similar free energies at room temperature: (i) a previously reported, ordered R3 polymorph stabilized upon drying and transforming first to R3c symmetry near 313 K and then to a similarly packed but disordered I43d polymorph near 353 K and (ii) a disordered Fm3 polymorph that initially appears from the disordered I43d polymorph near 513 K along with another disordered high-temperature P63mc polymorph. Quasielastic neutron scattering results indicate that the CB11H12− anions in the disordered phase at 560 K are undergoing isotropic rotational diffusion, with a jump correlation frequency [1.19(9) × 1011 s−1] in line with those for the lighter-metal analogues.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Bridging the gap between simulated and experimental ionic conductivities in lithium superionic conductors

Lithium superionic conductors (LSCs) are of major importance as solid electrolytes for next-generation all-solid-state lithium-ion batteries. While ab initio molecular dynamics have been extensively applied to study these materials, there are often large discrepancies between predicted and experimentally measured ionic conductivities and activation energies due to the high temperatures and short time scales of such simulations. Here, we present a strategy to bridge this gap using moment tensor potentials (MTPs). We show that MTPs trained on energies and forces computed using the van der Waals optB88 functional yield much more accurate lattice parameters, which in turn leads to accurate prediction of ionic conductivities and activation energies for the Li 0·33 La 0·56 TiO 3 , Li 3 YCl 6 and Li 7 P 3 S 11 LSCs. NPT MD simulations using the optB88 MTPs also reveal that all three LSCs undergo a transition between two quasi-linear Arrhenius regimes at relatively low temperatures. This transition can be traced to an increase in the number and diversity of diffusion pathways, in some cases with a change in the dimensionality of diffusion. Furthermore, this work presents not only an approach to develop high accuracy MTPs, but also outlines the diffusion characteristics for LSCs which is otherwise inaccessible through ab initio computation.

25 ENERGY STORAGE↗
DOE OSTI2022

Strongly Anharmonic Phonons and Their Role in Superionic Diffusion and Ultralow Thermal Conductivity of Cu 7 PSe 6

We report the quest for advanced superionic materials requires understanding their complex atomic dynamics, but detailed studies of the interplay between lattice vibrations and ionic diffusion remain scarce. Here inelastic and quasielastic neutron scattering measurements in the superionic argyrodite Cu 7 PSe 6 are reported, combined with molecular dynamics (MD) based on ab initio and machine-learned potentials, providing critical insights into the atomistic mechanisms underlying fast ion conduction. The results reveal how long-range Cu diffusion is limited by intercluster hopping, controlled by selective anharmonic phonons of the crystalline framework. Further, the Green–Kubo simulations reproduce the ultralow lattice thermal conductivity and identify contributions from mobile ions, phonons, and their cross-correlations. The mode resolved analysis shows that the thermal conductivity is dominated by low-energy acoustic phonon modes of the overall crystal framework. The analysis of mode-resolved spectral functions further show that vibrational modes with significant Cu contributions are strongly damped, corresponding to the breakdown of associated phonon quasiparticles. These results highlight the importance of strongly anharmonic effects in superionic systems, in which the traditional quasiharmonic phonon picture is insufficient, and pave the way toward combining machine-learning accelerated simulations with neutron scattering experiments to rationalize the complex atomic dynamics underlying ionic and thermal transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Microscopic Mechanisms of Superionic Na-ion Conductivity in Crystalline and Amorphous NaMOCl 4 (M = Nb, Ta) Solid Electrolytes

Sodium-ion solid electrolytes offer a sustainable route toward next-generation batteries, but few match the performance of their lithium counterparts. Halide-based NaMOCl 4 (M = Nb, Ta) has recently emerged as a promising analogue to LiMOCl 4 , yet its structure–transport relationships remain unclear due to poor crystallinity in experiments. Here, we combine density functional theory and machine-learned molecular dynamics to reveal that crystalline NaMOCl 4 exhibits negligible room-temperature conductivity with high activation barriers arising from vacancy-mediated diffusion below an order–disorder transition. Above this transition, rotational and translational motion of the [MO 2/2 Cl 4 – ] ∞ chains create new Na sites and enhances transport. In contrast, the amorphous phase inherently supports facile, three-dimensional Na diffusion through dynamic framework flexibility. These results show that ordered crystalline phases hinder ionic transport, while disorder – either thermally induced or structural – facilitates it, revising prior assumptions from the Li system and providing design principles for high-conductivity Na halide electrolytes.

Wei, Grace [University of California, Berkeley, CA↗
DOE OSTI2017

High conducting oxide--sulfide composite lithium superionic conductor

A solid electrolyte for a lithium-sulfur battery includes particles of a lithium ion conducting oxide composition embedded within a lithium ion conducting sulfide composition. The lithium ion conducting oxide composition can be Li.sub.7La.sub.3Zr.sub.2O.sub.12 (LLZO). The lithium ion conducting sulfide composition can be .beta.-Li.sub.3PS.sub.4 (LPS). A lithium ion battery and a method of making a solid electrolyte for a lithium ion battery are also disclosed.

25 ENERGY STORAGE↗
DOE OSTI2023

Degradation of Lithium Iron Phosphate Sulfide Solid-State Batteries by Conductive Interfaces

The superionic solid-state argyrodite electrolyte Li 6 PS 5 Br can improve lithium and lithium-ion batteries' safety and energy density. Despite many reports validating the conductivity of this electrolyte, it still suffers from passivating electrode degradation mechanisms. At first analysis, lithium iron phosphate (LFP) should be more thermodynamically stable in contact with sulfide electrolytes. However, without substantial improvements to interfacial engineering, we find that LFP is not inherently stable against Li 6 PS 5 Br. We hypothesize argyrodite oxidation favorably competes with LFPAs delithiation, insulating the electrolyte-electrode interface and causing large overpotential losses. We show that compared to LiNi x Mn y Co z O 2 , LFP has no actual electrochemical stability advantage despite operating at a lower voltage. We utilize tender energy XAS and XPS to show that chemical reactions occur between LFP and the Li 6 PS 5 Br solid electrolyte and these reactions are exacerbated by cycling. We also show that electrochemical degradation occurs at the interface between the solid electrolyte ion conductor and any electron conductor, namely the active material and carbon additives. We further demonstrate that LiNbO 3 cathode coatings on LFP can delay electrochemical degradation by electronically insulating the LFP-sulfide electrolyte interface but not prevent its occurrence at the carbon-electrolyte interface.

25 ENERGY STORAGE↗
DOE OSTI2025

Correction to “Stacking Faults Assist Lithium-Ion Conduction in a Halide-Based Superionic Conductor”

A typographical error needs to be corrected in the Results section, subsection “2.5. Evaluation of Li + Ion Conduction Properties”, fourth paragraph, where the activation energy barriers derived from PFG-NMR were swapped for components 1 and 2, for both BM-LYC and SS-LYC. The same error should also corrected in the second paragraph of the Discussion section.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2018

In-situ investigation of pressure effect on structural evolution and conductivity of Na 3 SbS 4 superionic conductor

Sulfide-based conductors are one class of the most promising solid electrolytes for next-generation of all-solid-state batteries due to their advantages on high ionic conductivity and favorable mechanical properties of easy densification. Besides new material chemistry to be explored, understanding the pressure effect on structure and property is equally important from both fundamental and practical considerations, as pressure is one way to tune the properties of such solid electrolytes. Here we address the pressure-driven structural evolution and conductivity change of Na 3 SbS 4 solid electrolyte through the integration of molecular dynamics (MD) simulation and in-situ experiments. Theoretical calculation predicts that no phase transition happens to tetragonal Na 3 SbS 4 under 10 GPa isotopically pressure. Synchrotron X-ray diffraction and Raman results confirm that Na 3 SbS 4 keeps stable tetragonal structure but shows anisotropic compressibility along different directions. After pressure release, the ionic conductivity of Na 3 SbS 4 increases by four folds to 1.6 mS cm -1 , which is derived from the dramatic decrease of grain boundary resistance.

42 ENGINEERING↗
DOE OSTI2024

Investigation of Low-Energy Lattice Dynamics and Their Role in Superionic Na Diffusion and Ultralow Thermal Conductivity of Na 3 PSe 4 as a Solid-State Electrolyte

The atomic dynamics of Na 3 PSe 4 were investigated using a combination of neutron scattering experiments and ab initio and machine-learned molecular dynamics simulations to probe the interplay of fast ionic diffusion with atomic vibrations (phonons) of the host lattice. Our results reveal the existence of low-energy vibrational modes, simultaneously involving motions of Na + ions and framework polyanion subunits, and show that these modes become strongly overdamped in the superionic regime as they couple with the Na + hopping process. In particular, the Na+ migration energy landscape is strongly impacted by low-energy phonons derived from a soft acoustic branch of the host lattice, which modulates the diameter of the Na + diffusion channel at the bottleneck. We find that an additional factor for the enhanced Na + conductivity in Na 3 PSe 4 is the presence of Na-vacancies, which also affect the low-frequency dynamics and thermal vibration amplitudes, pointing to an interplay between Na + vacancies and host dynamics, jointly enhancing ionic diffusivity. Finally, we investigate the origin of ultralow thermal conductivities in Na 3 PSe 4 and Na 3 PS 4 using Green–Kubo simulations and find that low-energy acoustic phonon modes of the overall crystal framework provide a dominant contribution to the thermal conductivity.

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

Anharmonic lattice dynamics and superionic transition in AgCrSe 2

Intrinsically low lattice thermal conductivity ( κ l a t ) in superionic conductors is of great interest for energy conversion applications in thermoelectrics. Yet, the complex atomic dynamics leading to superionicity and ultralow thermal conductivity remain poorly understood. Here, we report a comprehensive study of the lattice dynamics and superionic diffusion in A g C r S e 2 from energy- and momentum-resolved neutron and X-ray scattering techniques, combined with first-principles calculations. Our results settle unresolved questions about the lattice dynamics and thermal conduction mechanism in A g C r S e 2 . We find that the heat-carrying long-wavelength transverse acoustic (TA) phonons coexist with the ultrafast diffusion of Ag ions in the superionic phase, while the short-wavelength nondispersive TA phonons break down. Strong scattering of phonon quasiparticles by anharmonicity and Ag disorder are the origin of intrinsically low κ l a t . The breakdown of short-wavelength TA phonons is directly related to the Ag diffusion, with the vibrational spectral weight associated to Ag oscillations evolving into stochastic decaying fluctuations. Furthermore, the origin of fast ionic diffusion is shown to arise from extended flat basins in the energy landscape and collective hopping behavior facilitated by strong repulsion between Ag ions. These results provide fundamental insights into the complex atomic dynamics of superionic conductors.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Lithium Oxide Superionic Conductors Inspired by Garnet and NASICON Structures

Abstract The key component in lithium solid‐state batteries (SSBs) is the solid electrolyte composed of lithium superionic conductors (SICs). Lithium oxide SICs offer improved electrochemical and chemical stability compared with sulfides, and their recent advancements have largely been achieved using materials in the garnet‐ and NASICON (sodium superionic conductor)‐ structured families. In this work, using the ion‐conduction mechanisms in garnet and NASICON as inspiration, a common pattern of an “activated diffusion network” and three structural features that are beneficial for superionic conduction: a 3D percolation Li diffusion network, short distances between occupied Li sites, and the “homogeneity” of the transport path are identified. A high‐throughput computational screening is performed to search for new lithium oxide SICs that share these features. From this search, seven candidates are proposed exhibiting high room‐temperature ionic conductivity evaluated using ab initio molecular dynamics simulations. Their structural frameworks including spinel, oxy‐argyrodite, sodalite, and LiM(SeO 3 ) 2 present new opportunities for enriching the structural families of lithium oxide SICs.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Mechanistic insights into superionic thioarsenate argyrodite solid electrolytes via machine learning interatomic potentials

The lithium argyrodite sulfide solid electrolyte Li 6 PS 5 Cl has attracted considerable interest for all-solid-state batteries owing to its high ionic conductivity, which can be further enhanced through ionic substitution. Although a variety of substitutions have been investigated, thioarsenate argyrodites remain comparatively underexplored. Here, we systematically investigate the phase stability and Li-ion conduction mechanisms in superionic Br-incorporated thioarsenate argyrodites using first-principles calculations and molecular dynamics simulations based on machine learning interatomic potentials (MLIPs). Systematic variation of S/Br site inversion reveals that an optimal degree of anion disorder significantly enhances inter-cage connectivity and facilitates long-range Li-ion diffusion. Configurational entropy serves as an effective quantitative descriptor of anion disorder, exhibiting a strong correlation with ionic conductivity. While greater anion disorder induced by site inversion and higher Br content enhances ionic conductivity up to 50 mS cm −1 , it simultaneously reduces structural stability. This trade-off results in an optimal window in which a moderate level of disorder yields conductivities exceeding 20 mS cm −1 while maintaining synthetic feasibility. In conclusion, this work highlights the reliability and efficiency of MLIPs for elucidating ion-transport mechanisms and accelerating the design of novel superionic argyrodites.

Jang, Myeongcho [Korea Institute of Science and Te↗
DOE OSTI2018

Experimental evidence for superionic water ice using shock compression

In stark contrast to common ice, Ih, water ice at planetary interior conditions has been predicted to become superionic with fast- diffusing (that is, liquid-like) hydrogen ions moving within a solid lattice of oxygen. Likely to constitute a large fraction of icy giant planets, this extraordinary phase has not been observed in the laboratory. Here, we report laser-driven shock-compression experiments on water ice VII. Using time-resolved optical pyrometry and laser velocimetry measurements as well as sup- porting density functional theory–molecular dynamics (DFT-MD) simulations, we document the shock equation of state of H 2 O to unprecedented extreme conditions and unravel thermodynamic signatures showing that ice melts near 5,000 K at 190 GPa. Furthermore, optical reflectivity and absorption measurements also demonstrate the low electronic conductivity of ice, which, combined with previous measurements of the total electrical conductivity under reverberating shock compression, provides experimental evidence for superionic conduction in water ice at planetary interior conditions, verifying a 30-year-old prediction.

08 HYDROGEN↗