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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 OSTI2025

Computational and experimental analysis of structural and Thermophysical properties of LiX-KX (X = chloride, iodide, or bromide) molten salts

Molten salts containing lithium (Li) and potassium (K) halides, including chlorides (Cl), bromides (Br), and iodides (I), are pivotal in advanced technological applications including nuclear reactor technologies, thermal batteries, and industrial pyrochemical processes. Despite their significance, the availability of the temperature-dependent structural and thermophysical properties of these molten salts remain scarce. Here, this study addresses this knowledge gap by predicting and measuring the key properties such as coordination number, radial distribution function, density, heat capacity, and volumetric thermal expansion of molten LiI-KI, LiBr-KBr and LiCl-KCl eutectic mixtures. Utilizing ab initio molecular dynamics (AIMD) simulations, we predict these properties of LiX-KX (X=Br,I, Cl) across various temperatures, with chlorides as a benchmark. Experimental measurements using Archimedes methods and Differential Scanning Calorimetry validate the densities and heat capacities of these molten salts. Our comprehensive analysis of the structural and thermophysical properties provides critical insights into the behavior of these molten salts at various temperatures, enhancing the understanding necessary for their application in advanced technologies.

36 - MATERIALS SCIENCE↗
DOE OSTI2023

Highly Conductive Iodine and Fluorine Dual-Doped Argyrodite Solid Electrolyte for Lithium Metal Batteries

Sulfide-type argyrodite solid electrolytes (SEs) with halide doping have attracted serious interest. Although other halides such as Cl and Br have been found to enhance Li-ion transport in argyrodites, the direct synthesis of efficiently conductive Li 6 PS 5 I without postprocessing has rarely been investigated. In this work, we report the one-step synthesis of highly conductive Li 6 PS 5 I with an impressive ionic conductivity of 2.5 × 10 –4 S cm –1 at room temperature through a solvent-based method. Moreover, by introducing F – to partially replace I – , hybrid-doped argyrodites Li 6 PS 5 F x I 1–x (x = 0.25, 0.5, 0.75) have been synthesized. Li 6 PS 5 F 0.25 I 0.75 achieves the highest conductivity of 3.5 × 10 –4 S cm –1 due to the energetic preference for anion-disordering among F – /I – and S 2– , which facilitate faster Li transport as supported by density functional theory (DFT) calculations. With higher F content in argyrodites, Li 6 PS 5 F 0.75 I 0.25 displays the best electrochemical stability toward Li metal, as evidenced by long-term stable cycling in Li symmetric cells up to 1100 h. Solid-state Li metal batteries with an active cathode of Li 4 Ti 5 O 12 (LTO) display an initial specific capacity of 140 mAh g –1 and remain at 105 mAh g –1 after 200 cycles, suggesting great battery cycling performance. Furthermore, this research has developed new compositions in the argyrodite SE family which could lead to advancements in the development of solid-state Li metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

Enabling Conversion-Type Iron Fluoride Cathode by Halide-Based Solid Electrolyte

The practical application of low-cost and energy-dense iron fluoride cathodes has been hindered by the first cycle electrochemical irreversibility, cycling instability, and large voltage hysteresis. Here, we report that these challenges may be overcome by the utilization of halide-based solid electrolytes (SEs). The excellent electrochemical stability of halide-based SEs enables a complete conversion and deconversion of FeF 2 which cannot be achieved with sulfide-based SEs. Due to restricted and reversible decomposition of SE, prevention of Fe dissolution, mechanical confinement of active material, as well as improved electrode kinetics, solid-state FeF 2 cathode with halide-based SE demonstrated superior electrochemical performance compared with FeF 2 electrodes in liquid electrolytes, with a high 1st cycle coulombic efficiency (~100 %), high specific capacity (~600 mAh/g), long cycle life (>100 cycles) and high-rate performance (up to 2C). In conclusion, our results suggest solidifying the batteries may be a viable approach to addressing the long-standing key challenges of iron fluoride cathodes.

25 ENERGY STORAGE↗
DOE OSTI2022

Modeling assisted synthesis of Zr-doped Li 3-x In 1-x Zr x Cl 6 with ultrahigh ionic conductivity for lithium-ion batteries

All-solid-state lithium-ion batteries (ASSLBs) are an important milestone for the future of energy storage because of their capability of impressive energy density and outstanding safety. However, oxide and sulfide solid-state electrolytes (SSEs) suffer from either low ionic conductivity or poor chemical stability. In contrast, halide-based SSEs, are promising as candidate materials owing to high conductivity, good stability, and broad cathode compatibility. Though element doping of the SSEs is an effective and common approach to further improve their electrochemical properties, dopant exploration and optimization through solely experimental trials are both costly and time-consuming. For this aspect, computational simulations for dopant element and concentration screening are adopted in this research and zirconium is selected as a suitable dopant for Li 3 InCl 6 . Further, the synthesized Li 2.75 In 0.75 Zr 0.25 Cl 6 exhibited Li ionic conductivity of 5.82 x 10 -3 Scm -1 at room temperature, which is the highest among reported halide SSEs. The ASSLB formed with Li 2 CoO 2 -Li 2.75 In 0.75 Zr 0.25 Cl 6 -Li/In delivers a high initial capacity of 129.3 mAh∙g -1 . Conclusively, this work provides an effective approach which combines computational modeling and experimental verification for the development of halide SSEs with improved stability and conductivity. The successful design approach and compelling results provide further possibilities and capabilities in future SSE research.

25 ENERGY STORAGE↗
DOE OSTI2025

In-situ formation of stable interface towards Li-in anode for halide solid-state electrolyte

Halide-based solid-state electrolytes (SSEs) are promising candidates for next-generation all-solid-state lithium batteries (ASSLBs) due to their high ionic conductivity and chemical stability. However, their poor interfacial compatibility with lithium metal anode and Li-In alloy significantly hinder practical application due to the requirement for a protective interlayer. In this study, a novel approach to overcome this limitation is presented by introducing iron (Fe) doping into Li 3 InCl 6 (LIC), which enables direct and stable contact with lithium-indium (Li-In) metal without a protective interlayer. Thermodynamic and computational analyses identified Fe 3+ as a suitable dopant based on its similar reduction potential to In 3+ and structural compatibility within the halide lattice. The synthesized 10 at. % Fe-doped LIC exhibits high phase purity, retained ionic conductivity, and notably improved interfacial stability. Full-cell tests using Fe-LIC achieve over 300 cycles with 80 % capacity retention. At the same time, symmetric Li-In/ Fe-LIC/ Li-In cells sustain over 500 h of operation, representing the first reported long-term cycling of LIC-based ASSLB without a protective interlayer. In conclusion, this work establishes Fe doping as an effective strategy to stabilize halide SSEs of In system against Li-In alloy, thereby simplifying cell architecture and advancing the development of safer, high-performance halide-based solid-state electrolytes.

Halide-based solid-state electrolytes↗
DOE OSTI2020

An Evaluation of Energy Storage Cost and Performance Characteristics

The energy storage industry continues to expand globally as costs continue to fall and opportunities in consumer, transportation and grid applications are defined. As the rapid evolution of the industry continues, it has become increasingly important to understand how varying technologies compare in terms of cost and performance. This paper defines and evaluates cost and performance parameters of six battery energy storage technologies (BESS) - lithium-ion batteries, lead-acid batteries, redox flow batteries, sodium-sulfur batteries, sodium metal halide batteries, and zinc-hybrid cathode batteries - four non-BESS storage technologies - pumped storage hydropower, flywheels, compressed air energy storage, and ultracapacitors - and combustion turbines. Cost and performance information was compiled based on an extensive literature review, conversations with vendors and stakeholders, and costs of systems procured at sites across the United States. Detailed cost and performance estimates are presented for 2018 and projected out to 2025. Annualized costs were also calculated for each technology.

Mongird, Kendall↗
DOE OSTI2023

Thermodynamic controls on the synthesis, structure and reactivity of materials for energy (Final Report)

The major objectives of this renewal proposal, now entitled “Thermodynamic Controls on the Synthesis, Structure and Reactivity of Materials for Energy,” are: (a) to advance and use unique calorimetric capabilities to determine the energetics of materials relevant to energy applications, with an emphasis on new materials, (b) to understand, in terms of both macroscopic energetics and microscopic structure and bonding, the interplay of defect chemistry, oxidation-reduction and size effects at the nanoscale in determining the properties of functional oxide materials and of new classes of non-oxide materials. Recent developments have generated great excitement in organic-inorganic hybrid materials such as the alkylammonium lead halide perovskites. Our current work has emphasized fluorite-based solid electrolytes, perovskites and lithium battery materials. The systematic trends seen enable a more holistic view of the relation of thermodynamics to materials discovery and synthesis. The proposed work more explicitly targets thermodynamic controls on metastability, energy landscapes, surface and nanoscale effects, and pathways of synthesis and decomposition. This project is leveraged by many U.S. and international collaborations that both extend the science and provide opportunities for work in a diverse global setting.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Thermodynamic controls on the synthesis, structure and reactivity of materials for energy (Final Report)

The major objectives have been: a) to advance and use unique calorimetric capabilities to determine the energetics of oxide and other materials having possible energy applications, with an emphasis on new materials for batteries, fuel cells and solar energy conversion, b) to understand, in terms of both macroscopic energetics and microscopic structure and bonding, the interplay of defect chemistry, oxidation-reduction, and size effects at the bulk and nanoscale in determining materials properties. This project emphasizes mixed ionic-electronic conduction materials containing transition metals of variable valence, especially perovskites and lithium containing phases, with M = Mn, Fe, Co, Ni. The thermochemistry of new families of complex halide, chalcogenide, nitride and hybrid (organic-inorganic) perovskite materials were explored. The major and unique technique employed is high temperature oxide melt solution calorimetry, with careful attention given to materials synthesis and characterization. The thermochemical studies will be coupled with structural studies, especially to characterize order-disorder phenomena by in situ high temperature diffraction techniques.

14 SOLAR ENERGY↗
DOE OSTI2025

Chemical Bond Covalency in Superionic Halide Solid‐State Electrolytes

Abstract Halide solid‐state electrolytes (SSEs) are promising superionic conductors with high oxidative stability and ionic conductivity, making them attractive for all‐solid‐state lithium‐ion batteries. However, most studies have focused on ion‐stacking structures, overlooking the role of bond characteristics in ionic transport. Here, we investigate bond dynamics and the superionic transition (SIT) in bromide electrolyte, Li 3 InBr 6 , using synchrotron X‐ray techniques and ab initio molecular dynamics (AIMD) simulations. We demonstrate that the SIT in halide SSEs is driven by a thermally induced transition in bonding character (ionic to covalent) rather than a change in crystal phase. AIMD simulations further reveal enhanced Li⁺ diffusion and collective anion motion at elevated temperatures. Expanding our study to Li 3 LnBr 6 (Ln = Gd, Tb, Ho, Tm, and Lu), we confirm the widespread occurrence of SIT in this material class, with Li 3 GdBr 6 exhibiting the highest ionic conductivity (5.2 mS cm −1 at 298 K). More importantly, the ionic‐covalent transition is highly tunable through electrolyte modifications, such as cation/anion substitution and synthesis methods. Our findings provide a new perspective on ionic transport, highlighting the critical role of chemical bond characteristics in halide SSEs.

Chemistry↗
DOE OSTI2020

A new halospinel superionic conductor for high-voltage all solid state lithium batteries

We report a new Li-superionic chloride, Li 2 Sc 2/3 Cl 4 , that crystallizes in a disordered spinel structure, and exhibits an ionic conductivity of 1.5 mS cm –1 with a low activation energy barrier for Li + ion diffusion of 0.34 eV. Here, this material is the first spinel-type superionic halide. Structural elucidation via powder neutron diffraction reveals a significantly disordered Li + -ion distribution over available tetrahedral and octahedral sites within the lattice, forming an infinitely 3D connected Li + ion diffusion pathway comprised of face-sharing octahedra and tetrahedra. Due to the high oxidative stability of Li 2 Sc 2/3 Cl 4 , all solid state lithium batteries employing Li 2 Sc 2/3 Cl 4 and high voltage cathodes (LiCoO 2 , LiNi 0.6 Mn 0.2 Co 0.2 O 2 or high-Ni LiNi 0.85 Mn 0.1 Co 0.05 O 2 ) – without any coating – exhibit excellent electrochemical performance up to 4.6 V in terms of capacity retention and cycle life.

25 ENERGY STORAGE↗
DOE OSTI2021

The efficacy of Lewis affinity scale metrics to represent solvent interactions with reagent salts in all-inorganic metal halide perovskite solutions

Solvents employed in the solution processing of metal halide perovskites are known to play a key role in defining the morphology and properties of the resulting thin film, and thus the performance of perovskite solar cell devices. Accurate metrics are needed that are capable of differentiating among candidates, finding solvents that adequately solubilize the various precursor species in solution and facilitate the nucleation and growth of these materials. Existing metrics such as the unsaturated Mayer bond order (UMBO) and the Gutmann donor number (DN) have been tested for lead iodide perovskite systems; but there has yet to be a comprehensive study on their transferability to lead-free perovskite solutions. Here, we use ab initio methods (density functional theory) and regression analysis tools to study the usefulness of DN and BF 3 affinity scales in this regard. We compared the relative effectiveness of these scales to describe interactions between solvents and BXn perovskite salts of lead (Pb 2+ ), tin (Sn 2+ and Sn 4+ ), germanium (Ge 2+ ), bismuth (Bi 3+ ), and antimony (Sb 3+ and Sb 5+ ). The DN proved to be a better representation than the BF 3 of such interactions, reflecting the closer similarity of these species to the “parent” SbCl 5 Lewis acid than to BF 3 . In addition, we have uncovered the usefulness of the lithium cation affinity metric (LCA) to describe the strength of interactions between solvents and A-site cations (e.g. Na + , K + , Rb + and Cs + ) in all-inorganic metal halide perovskite solutions. We find that the coordination strengths of solvents towards species in all-inorganic metal halide perovskite solutions are best described by two different metrics with distinct modes of action: DN differentiates among BX n salt complexes, and LCA among A-site cation species. This revelation can help guide the choice of solvent to optimize processing conditions. It also emphasizes the importance of selecting solvents whose DN and LCA optimize coordination to key Lewis acid species in all-inorganic perovskite solutions.

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

Lowering the Activation Barriers for Lithium-Ion Conductivity through Orientational Disorder in the Cyanide Argyrodite Li6PS5CN

Rapid advancements in safe and high-energy-density energy storage are predicated on identifying new solid-state ion conductors with low activation energies and high ionic conductivities for all-solid-state battery technologies. Halide argyrodites are among some of the top candidates for solid-state electrolytes, as they can achieve ionic conductivities that approach liquid electrolytes. Incorporating dynamic pseudohalide species in argyrodite solid electrolytes presents an exciting opportunity to exploit lattice dynamics as a design principle to modulate the ion conduction properties of solid-state ion conductors. In the present study, we have prepared the new argyrodite Li 6 PS 5 CN containing orientationally disordered cyanide ions. The new cyanide argyrodite Li 6 PS 5 CN exhibits an activation barrier to Li-ion transport of 471 ± 25 meV and a room-temperature ionic conductivity of 6(2) × 10 –5 S cm –1 in comparison to the activation barrier of 502 ± 16 meV and an ionic conductivity of 2.3(1) × 10 –4 S cm –1 measured for the bromide analogue Li 6 PS 5 Br. Structural studies of both compounds by high-resolution X-ray diffraction indicate that Li 6 PS 5 CN and Li 6 PS 5 Br adopt nearly identical crystal structures with similar lattice parameters, which indicates that lower activation barriers in Li 6 PS 5 CN arise due to the cyanide ion itself rather than due to changes in the geometry of conduction pathways in the local lithium environment. The orientational disorder of the quadrupolar cyanide ion in Li 6 PS 5 CN points to a complex interplay of lattice polarizability and molecular dynamics that lower the activation barrier for lithium-ion conductivity in the cyanide argyrodite.

25 ENERGY STORAGE↗
DOE OSTI2022

A mechanistic study of the dopant-induced breakdown in halide perovskites using solid state energy storage devices

Doping halide perovskites (HPs) with extrinsic species, such as alkali metal ions, plays a critical, albeit often elusive role in optimising optoelectronic devices. Here, we use solid state lithium ion battery inspired devices with a polyethylene oxide-based polymer electrolyte to dope HPs controllably with lithium ions. We perform a suite of operando material analysis techniques while dynamically varying Li doping concentrations. We determine and quantify three doping regimes; a safe regime, with doping concentrations of <10 20 cm –3 (2% Li : Pb mol%) in which the HP may be modified without detrimental effect to its structure; a minor decomposition regime, in which the HP is partially transformed but remains the dominant species; and a major decomposition regime in which the perovskite is superseded by new phases. We provide a mechanistic description of the processes mediating between each stage and find evidence for metallic Pb (0) , LiBr and LiPbBr 2 as final decomposition products. Combining results from synchrotron X-ray diffraction measurements with in situ photoluminescence and optical reflection microscopy studies, we distinguish the influences of free charge carriers and intercalated lithium independently. We find that the charge density is equally as important as the geometric considerations of the dopant species and thereby provide a quantitative framework upon which the future design of doped-perovskite energy devices should be based.

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

Materials design of sodium chloride solid electrolytes Na3MCl6 for all-solid-state sodium-ion batteries

All-solid-state sodium-ion batteries have attracted increasing attention owing to the low cost of sodium and the enhanced safety compared to conventional Li-ion batteries. Recently, halides have been considered as promising solid electrolytes (SEs) due to their favorable combination of high ionic conductivity and chemical stability against high-voltage cathode materials. Although a wide variety of lithium chloride SEs, Li 3 MCl 6 , have been developed for high-voltage all-solid-state batteries, only a limited number of sodium chloride SEs have been reported. This study aims to offer a material design insight for the development of sodium chloride SEs through systematic assessment of the phase stability, electrochemical stability, and transport properties of novel Na 3 MCl 6 SEs. Structural calculations indicate that Na 3 MCl 6 exhibits trigonal $P\bar{3}$1c, monoclinic P2 1 /n, and trigonal $R\bar{3}$ phases, and the stable phase of Na 3 MCl 6 is dependent on the type and ionic radius of M. Na 3 MCl 6 typically exhibits a high oxidation potential, demonstrating good electrochemical stability against cathodes. The bond-valence site energy and ab initio molecular dynamics calculations revealed that Na 3 MCl 6 with P2 1 /n and $R\bar{3}$ phases showed low ionic conductivity, while the $P\bar{3}$1c phase slightly improved the ionic conductivity of Na 3 MCl 6 . The formation of Na vacancies by aliovalent substitution considerably increased the ionic conductivity up to four orders of magnitude for pristine Na 3 MCl 6 , exhibiting ~10 –5 S cm –1 for trigonal $P\bar{3}$1c and $R\bar{3}$ phases. The formation of defects could further enhance the ionic conductivity of Na 3 MCl 6 , and the optimization of defect type and ratio can be helpful in developing superionic Na chloride SEs. The material design of Na 3 MCl 6 in this study will provide fundamental guidelines for the development of novel sodium halide SEs for all-solid-state sodium-ion batteries.

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

Tl+-based and mixed halide A3B2X9-type scintillators

Inorganic halides (e.g., inorganic halide scintillators) of the general formula A3B2X9, including inorganic halides comprising thallium monovalent cations and/or combinations of different halides, are described. Radiation detectors including the inorganic halide scintillators and methods of using the detectors to detect high energy radiation are also described. In some cases, the scintillators can include a gadolinium cation, a boron cation, a lithium cation, a chloride ion, or combinations thereof and the scintillator can be used to detect neutrons.

Rutstrom, Daniel↗
DOE OSTI2025

Design of Sodium Chalcohalide Solid Electrolytes with Mixed Anions for All‐Solid‐State Sodium‐Ion Batteries

Solid-state sodium-ion batteries (SSNIBs) have emerged as a promising alternative to lithium-ion systems for grid-scale energy storage, owing to sodium's abundance and the improved safety of solid-state designs. Among various solid-state electrolytes (SSEs), halide-based Na + SSEs offer high electrochemical stability but are limited by low ionic conductivity and poor thermal stability. Herein, a novel class of sodium hafnium chalcohalide SSEs is reported with a dual-anion (S 2− /Cl − ) framework, with a high ionic conductivity of 4.5 × 10 −4 S cm −1 . The incorporation of sulfur enhances Na⁺ mobility by reducing the migration barrier through increased anion polarizability and expanded diffusion pathways. Additionally, S 2− contributes to stronger interatomic bonding, leading to higher cohesive energy density, improved thermal stability, and mechanical robustness. These SSEs exhibit minimal sulfur oxidation and excellent chemical/electrochemical interface stability with different cathode materials, such as O3-layered NaNi 1/3 Fe 1/3 Mn 1/3 O 2 , P2/O3 layered Na 0.85 Mn 0.5 Ni 0.4 Fe 0.1 O 2 , and Na 3 V 2 (PO 4 ) 3 cathodes. As a result, SSNIBs with P2/O3 layered Na 0.85 Mn 0.5 Ni 0.4 Fe 0.1 O 2 employing the sodium hafnium chalcohalide SSEs demonstrate outstanding cycling performance, achieving a capacity retention of 88.5% after 200 cycles at 0.1 C. This study establishes a new design strategy for high-performance SSEs, demonstrating that mixed-anion frameworks offer a viable route to overcome the intrinsic limitations of single-anion electrolytes in next-generation SSNIBs.

DFT calculation↗
DOE OSTI2026

Distinct Melt Infusion Architectures of Antiperovskite Solid Electrolytes

Antiperovskite solid electrolytes are an emerging class of lithium‐ion conductors distinguished by their unusually low melting points, enabling scalable, low‐temperature processing routes not accessible to most solid electrolytes. In this work, we synthesize phase‐pure chloride (Cl), bromide (Br), and mixed halide (ClBr) variants of antiperovskites and investigate their ionic conductivities in both powder and hot‐pressed forms. Hot pressing significantly enhances conductivity across all compositions, while energy‐dispersive X‐ray spectroscopy (EDS) of the mixed halide system reveals halide surface migration during densification. We further investigate the melt‐infiltration behavior of these electrolytes into substrates relevant to solid‐state battery architectures, including Al and Cu current collectors, conventional NMC and LFP cathodes, and a foamed NMC cathode with a highly porous architecture. The foamed cathode enables deep and uniform electrolyte penetration, highlighting the role of electrode architecture in facilitating melt infiltration. Across all substrates, electrolyte halide chemistry strongly influences wetting behavior, penetration depth, and resulting microstructural morphology. Together, these results establish clear processing–structure relationships for melt‐infiltrated antiperovskite solid electrolytes and demonstrate how electrolyte chemistry and electrode architecture govern interfacial morphology during integration, providing practical guidelines for processing and structural design in solid‐state battery systems.

antiperovskite↗