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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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177 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Site Disorder Drives Cyanide Dynamics and Fast Ion Transport in Li 6 PS 5 CN

Halide argyrodite solid-state electrolytes of the general formula Li 6 PS 5 X exhibit complex static and dynamic disorder that plays a crucial role in ion transport processes. Here, we unravel the rich interplay between site disorder and dynamics in the plastic crystal argyrodite Li 6 PS 5 CN and the impact on ion diffusion processes through a suite of experimental and computational methodologies, including temperature-dependent synchrotron powder X-ray diffraction, AC electrochemical impedance spectroscopy, 7 Li solid-state NMR, and machine learning-assisted molecular dynamics simulations. Sulfide and (pseudo)halide site disorder between the two anion sublattices unilaterally improves long-range lithium diffusion irrespective of the (pseudo)halide identity, which demonstrates the importance of site disorder in dictating bulk ionic conductivity in the argyrodite family. Furthermore, we find that anion site disorder modulates the presence and time scales of cyanide rotational dynamics. Ordered configurations of anions enable fast, quasi-free rotations of cyanides that occur on time scales of 10 11 Hz at T = 300 K. In contrast, we find that cyanide dynamics are slow or frozen in Li 6 PS 5 CN when site disorder between the cyanide and sulfide sublattices is present at T = 300 K. We rationalize the observed differences in cyanide dynamics in the context of elastic dipole interactions between neighboring cyanide anions and local strain induced by the configurations of site disorder that may impact the energetic landscape for cyanide rotational dynamics. Through this study, we find that anion disorder plays a decisive role in dictating the extent and time scales of both lithium ion and cyanide dynamics in Li 6 PS 5 CN.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Porous and Amorphous Mn x Mo 3 S 13 Chalcogel Electrode for High-Capacity Conversion-Based Lithium-Ion Batteries

While Li-ion batteries (LIBs) are a leading energy storage technology, their energy densities are limited by the low capacity of conventional intercalation cathodes, driving interest in high energy-density Li–S batteries that make use of conversion chemistry. Achieving high capacity, reversibility, and cycle stability, and controlling volume changes in conversion batteries during the charge–discharge process, however, remains challenging. Here, in this study, we present a porous, amorphous, sulfide-based Mn x Mo 3 S 13 chalcogel, which concurrently offers high capacity and cycle stability. The solution-processable room temperature synthesized Mn x Mo 3 S 13 (x = 0.25) chalcogel exhibits a local structure that resembles the Mo 3 S 13 cluster with Mn 2+ distributed across the Mo 3 S 13 matrix, as determined by synchrotron X-ray pair distribution function (PDF) and extended X-ray absorption fine structure (EXAFS). Ab initio molecular dynamics (AIMD) simulations reveal that Mn 2+ incorporation shortens the polysulfide chain in the gel matrix compared to the Mo 3 S 13 chalcogel, while forming a coordination environment with disulfide groups, analogous to the experimental findings. A Li/Mn 0.25 Mo 3 S 13 half-cell delivers 897 mAh g –1 capacity during the first discharge and retains 571 mAh g –1 capacity after 100 cycles at a C/3 rate. Distribution of relaxation time (DRT) unveils a stable solid–electrolyte interphase (SEI) formation upon cycling that enables charge–discharge reversibility. Here, the enhanced capacity retention and cycle stability compared to those of the Li/Mo 3 S 13 cell are attributed to the reduced dissolution of active mass into the electrolyte, facilitated by the formation of shorter polysulfide chains within the Mn 0.25 Mo 3 S 13 structure and the strong affinity of Lewis-acidic Mn 2+ for polysulfide anions generated during the charge–discharge process of the Li/Mn 0.25 Mo 3 S 13 cell. Thus, this work illustrates a design principle of material for high-capacity and cycle-stable Li-metal sulfide batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Interfaces in all solid state Li-metal batteries: A review on instabilities, stabilization strategies, and scalability

With technological advancements in electrochemical energy storage systems increasing at a spectacular rate, batteries equipped with a lithium anode hold the key towards unlocking high energy densities. While lithium-ion batteries with layered anodes (e.g. graphite) and liquid organic electrolytes have been ubiquitous in portable electronics, electric vehicles, and grid applications, all solid-state batteries that use the combination of a lithium anode and a solid-state electrolyte (SSE) will further advance the present technology. The underlying challenge that limits the successful development of all solid-state batteries (ASSBs) is dictated largely by the highly reactive interfaces at the anode/SSE and the cathode/SSE interface. In this comprehensive review, we present an overview of the following: (i) characterization of the electrode/SSE interface via multimodal characterization, which include X-ray-, electron-, neutron-, optical-, and computation-based methods: (ii) parasitic reactions that occur from chemical, mechanical or electrochemical instabilities and interfacial engineering strategies for improving the stability of these interfaces classified by the class of inorganic SSEs (sulfide-, NASICON-, and garnet-type SSEs); (iii) laboratory-to-industry scale processing perspectives of SSEs; (iv) scalability and manufacturing aspects of current interfacial strategies; and (v) the prospects of all ASSBs within the context of extreme fast charging capability. Here, this review seeks to highlight key efforts in the field of ASSBs, by focusing particularly on stabilizing the electrode/SSE interfaces, which will help to bridge fundamental studies to technological relevance.

25 ENERGY STORAGE↗
DOE OSTI2025

Sulfide-Based Anode-Free Solid-State Batteries: Key Challenges and Emerging Solutions

Sulfide-based anode-free solid-state batteries (AFSSBs) have emerged as a transformative technology for next-generation energy storage, offering compelling advantages in energy density, safety, and manufacturing scalability. However, these batteries face significant challenges, particularly rapid capacity degradation that currently limits their practical implementation. This comprehensive review critically examines three fundamental issues affecting AFSSBs: nonuniform lithium nucleation on bare current collectors, unstable interfaces between plated lithium and sulfide electrolytes, and formation of interfacial voids during cycling. We systematically evaluate recent strategic advances in addressing these challenges, including metal seed coatings, conversion reaction-based compounds, and carbon-based interlayers. The review also analyzes the crucial role of advanced characterization techniques, from cryo-FIB-SEM to operando methods, in understanding failure mechanisms and validating improvement strategies. Finally, we present a forward-looking perspective on research directions necessary for commercialization. This work provides a thorough framework for understanding and advancing sulfide-based AFSSBs toward practical applications in next-generation energy storage systems.

25 ENERGY STORAGE↗
DOE OSTI2022

Elucidating the Determinants of Alkali Ionic Conductivity in Oxide and Sulfide Frameworks

The aim of this project is to elucidate the structural and chemical factors determining alkali conductivity in oxide and sulfide frameworks using large scale first principles calculations and topological analysis. The facile conduction of alkali ions in oxide and sulfide host structures is of critical importance in energy storage. Today, the dominant form of energy storage in portable electronics is the rechargeable alkali-ion battery, a device that functions entirely on the basis of the reversible transport of alkali ions. The Li+/Na+ conductivity of a cathode has a direct influence on the rate capability of a Li/Na-ion battery, i.e., the speed at which it can be charged and discharged. Alkali conductivity is arguably of even greater importance in the solid electrolytes currently being investigated for high safety, high energy all-solid-state batteries. The research performed in this project has provided critical new insights into the diffusion mechanisms in state-of-the-art alkali superionic conductors such as Li 7 P 3 S 11 , Li 3 OCl 1-x Br x anti-perovskite, argyrodite Li 6 PS 5 Cl. Two potential novel lithium superionic conductors (Li 3 Y(PS 4 ) 2 and Li 5 PS 4 Cl 2 ) with improved electrochemical stabilities were predicted. We have also conducted in-depth studies into alkali conduction in several important classes of electrodes, including the layered P2 NaMO 2 oxides and the highly promising novel disordered rock salt Li 3+x V 2 O 5 anode for high-rate applications. This project has resulted in more than 10 peer-reviewed articles in highly regarded journals as well as a new open-source software framework (pymatgen-analysis-diffusion) that is widely used by the materials research community for the study of diffusion in materials.

25 ENERGY STORAGE↗
DOE OSTI2021

An in situ generated polymer electrolyte via anionic ring-opening polymerization for lithium–sulfur batteries

The use of solid polymer electrolytes has previously proven to be an effective approach to address the lithium polysulfide dissolution and high electrode interfacial impedance of Li–S batteries via an in situ polymerization process. However, the conventional in situ synthesis employs a cationic ring-opening polymerization (CROP) of 1,3-dioxolane (DOL) catalyzed by a strong Lewis acid. New polymerization chemistry that is more compatible with Li–S chemistry needs to be developed to mitigate the disadvantages associated with the CROP process. Herein we report a new approach to in situ polymerize a set of new episulfide monomers in solution with LiTFSI salt via an anionic ring-opening polymerization (AROP). This new polymer system takes advantage of the inherent cell chemistry present in the Li–S cell through the nucleophilic lithium sulfides which are generated during the initial discharge cycle and act as the initiator for the polymerization. Additionally, their presence was shown to initiate the monomer solvents through AROP with no need for additional catalysts, rather than the more commonly utilized cationic systems which require an external Lewis acid catalyst. This work offers an important pathway toward in situ polymer electrolytes for Li–S batteries and offers a new avenue of exploration for polymer electrolyte synthesis.

25 ENERGY STORAGE↗
DOE OSTI2024

Crack‐Free Single‐Crystalline LiNiO 2 for High Energy Density All‐Solid‐State Batteries

Abstract Single‐crystalline layered oxide (LiNi 1‐ x ‐ y Mn x Co y O 2 ) cathodes have been found to exhibit exceptional electrochemical properties when coupled with various inorganic solid electrolytes (ISEs) in all‐solid‐state batteries (ASSBs). Their advantages stem from the robust morphological integrity with the absence of grain boundaries and the high electrochemical oxidative stability. Here, ASSBs featuring single‐crystalline LiNiO 2 (LNO) with the highest Ni content are reported, offering a high theoretical specific capacity of 275 mAh g ‐1 alongside a high average discharge voltage (3.7 V vs Li + /Li). Through a careful investigation, it is demonstrated that micron‐sized single‐crystalline LNO (µSC‐LNO) composite cathodes with a halide ISE exhibit a high initial discharge capacity of 205 mAh g ‐1 with an outstanding cycle performance over 200 cycles in room‐temperature ASSBs. The significance of engineering parameters is emphasized, such as particle size and specific density, in promoting a homogeneous and fast Li + transport within the composite cathodes. Furthermore, the formation of undesirable interphase between the halide ISE in the cathode and sulfide ISE separator is elucidated, which may be a critical factor impeding long‐term cyclability of ASSBs. This work provides insights into the design of composite cathodes for high‐energy‐density ASSBs.

Chemistry↗
DOE OSTI2021

All solid thick oxide cathodes based on low temperature sintering for high energy solid batteries

Solid-state batteries (SSBs) could significantly improve the safety and energy density over conventional liquid cells. One key enabling technology is the use of solid electrolytes. NASICON-type Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) is a very attractive solid-state electrolyte for the cathode side due to its high oxidation potential and high ionic conductivity. The usage, however, is limited by its large interfacial resistance against most of the cathode materials as well as the thermodynamic instability during high temperature sintering needed to achieve high mass density. Here we construct thin, percolative, and mixed conductive interphases through in situ low-melting-point liquid sintering. These mixed conductive interphases drastically improve the kinetics, leading to high-loading solid LATP/LiCoO 2 cathodes achieving capacity loading of up to ~6 mA h cm –2 . The technique is also applicable to Ni-rich cathode materials, achieving up to ~10 mAh cm –2 , which can lead to more than 400 W h kg –1 cells in SSBs. Furthermore, our composite cathodes show a ten-times and three-times area capacity improvement over the state-of-the-art cathodes using oxide and sulfide SSEs, respectively.

25 ENERGY STORAGE↗
DOE OSTI2021

Heavily Tungsten–Doped Sodium Thioantimonate Solid–State Electrolytes with Exceptionally Low Activation Energy for Ionic Diffusion

A strategy for modifying the structure of solid-state electrolytes (SSEs) to reduce the cation diffusion activation energy is presented. Two heavily W-doped sodium thioantimonate SSEs, Na 2.895 W 0.3 Sb 0.7 S 4 and Na 2.7 W 0.3 Sb 0.7 S 4 are designed, both exhibiting exceptionally low activation energy and enhanced room temperature (RT) ionic conductivity; 0.09 eV, 24.2 mS/cm and 0.12 eV, 14.5 mS/cm. At –15 °C the Na 2.895 W 0.3 Sb 0.7 S 4 displays a total ionic conductivity of 5.5 mS/cm. Here, the 30 % W content goes far beyond the 10–12 % reported in the prior studies, and results in novel pseudo-cubic or orthorhombic structures. Calculations reveal that these properties result from a combination of multiple diffusion mechanisms, including vacancy defects, strongly correlated modes and excessive Na-ions. An all-solid-state battery (ASSB) using Na 2.895 W 0.3 Sb 0.7 S 4 as the primary SSE and a sodium sulfide (Na 2 S) cathode achieves a reversible capacity of 400 mAh g –1 .

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

Heavily Tungsten-Doped Sodium Thioantimonate Solid-State Electrolytes with Exceptionally Low Activation Energy for Ionic Diffusion

A strategy for modifying the structure of solid-state electrolytes (SSEs) to reduce the cation diffusion activation energy is presented. Two heavily W-doped sodium thioantimonate SSEs, Na 2.895 W 0.3 Sb 0.7 S 4 and Na 2.7 W 0.3 Sb 0.7 S 4 are designed, both exhibiting exceptionally low activation energy and enhanced room temperature (RT) ionic conductivity; 0.09 eV, 24.2 mS/cm and 0.12 eV, 14.5 mS/cm. At –15 °C the Na 2.895 W 0.3 Sb 0.7 S 4 displays a total ionic conductivity of 5.5 mS/cm. The 30 % W content goes far beyond the 10–12 % reported in the prior studies, and results in novel pseudo-cubic or orthorhombic structures. Here, calculations reveal that these properties result from a combination of multiple diffusion mechanisms, including vacancy defects, strongly correlated modes and excessive Na-ions. An all-solid-state battery (ASSB) using Na 2.895 W 0.3 Sb 0.7 S 4 as the primary SSE and a sodium sulfide (Na 2 S) cathode achieves a reversible capacity of 400 mAh g –1 .

sodium metal battery (SMB)↗
DOE OSTI2026

Controlled lithium stripping enables a stable interface for long-cycling anode-free solid-state batteries

Anode-free solid-state batteries (AFSSBs) are a promising route toward achieving high energy density. In these cells, the anode contains no pre-stored lithium (Li). Instead, the entire Li inventory originates from the cathode and is freshly deposited onto a bare current collector during charging. However, achieving uniform and defect-free Li plating on this bare current collector remains a major challenge, often resulting in low Li plating/stripping efficiency and rapid capacity decay. Here, for the first time, operando neutron imaging is employed to visualize Li plating/stripping behavior in an anode-free full cell with LiNi0.82Mn0.07Co0.11O2 (NMC) as the cathode. Operando measurements reveal that complete stripping of Li leaves isolated Li residues on the current collector, which degrades the interfacial contact between the current collector and the solid-state electrolyte. To mitigate this interfacial issue and promote more uniform Li deposition, we implement a discharge-cutoff-voltage strategy that intentionally retains a thin residual Li layer after stripping. This preserved Li-containing interfacial reservoir not only improves interfacial contact but also serves as an in situ formed seed layer that enables more homogeneous subsequent Li plating. As a result, the optimized anode-free cell with limited stripping depth exhibits excellent long-term cycling stability, maintaining a discharge capacity of 112.1 mAh g−1 with a capacity retention of 80.6% and an average coulombic efficiency of approximately 99.9% after 500 cycles at 0.25 C. In contrast, the cell with a conventional discharge cutoff voltage of 2.8 V exhibits rapid capacity decay, retaining only 59.7 mAh g−1 after 50 cycles with a capacity retention of 40.7%. This work demonstrates that limiting deep stripping to preserve a thin Li-containing interfacial layer can effectively improve the cycling stability of sulfide-based AFSSBs.

Wang, Jiwei [Northeastern University, Boston]↗
DOE OSTI2021

Quantifying the chemical, electrochemical heterogeneity and spatial distribution of (poly) sulfide species using Operando SANS

In-situ and operando measurements are done to gain a better understanding of the precipitation mechanisms during charge and discharge in lithium sulfur batteries. A carbon felt networked with microfibers consisting of pores, 2 nm and smaller, is used as a freestanding sulfur host. Three different methods of sulfur infiltration are explored in order to determine the best one to fill most of the pores. It was identified to be a melt infiltration method in a vacuum oven, where the pores including the ultra-micropores, are successfully filled. In-situ electrochemical impedance spectroscopy measurements show a solid product formation occurring at the sulfur cathode, both during the high voltage plateau and at the end of discharge. In a 3-electrode EIS measurement, a similar solid product formation on the Li counter electrode due to its reaction with polysulfides is also observed. Operando small angle neutron scattering measurements show the solid product formation, in the carbon, both near the beginning and at the end of discharge, confirming the precipitation data via contrast changes as a function of charge and discharge. It is shown that Li 2 S precipitates in the pores at the beginning and the end of discharge, whereas S8 precipitates on the surface of the carbon felt. Finally, this lithium sulfur system shows both the quasi-solid-state and the solid-liquid-solid reactions in a typical ethereal electrolyte solution with a two-plateau discharge profile.

25 ENERGY STORAGE↗
DOE OSTI2025

Novel Superionic Na Conductors for Solid‐State Na batteries: Materials and Interface

This project aims to advance the fundamental understanding on how the cation or anion doping influence on the crystal structure, phase stability and ion transport of novel Na superionic conductors. Specifically, we focus on the Na 3-x A x SbS 4-y X y family solid electrolytes (A: cation dopant, X: anion dopant), a class of promising materials for all-solid-state sodium batteries owing to their high ionic conductivity and compositional tunability. By integrating materials synthesis, neutron scattering, and electrochemical characterization and theoretical simulations, this project sees to elucidate 1) how does the synthesis approaches (solid-state reaction, low-temperature reaction) on the phase purity and doping process; 2) how chemical doping (A: cation dopants such as Sn; X: anion dopants such as Se, F) modulate lattice dynamics and Na+ migration as well as interface stability toward Na metal. Specifically, this project’s proposed technology involves three objectives: (1) synthesize novel Na-ion conductors (anion or cation doped Na 3 SbS 4 ) with high phase purity and examine their structural features (e.g., phase stability); (2) understand Na-ion conductive properties of new Na-ion conductors through a combination of experimental characterizations and theoretical simulations; (3) investigate the interface stability of novel Na superionic conductors with electrode materials in solid-state Na batteries. These objectives will be achieved through combined experimental synthesis/characterizations and computational approaches. The obtained knowledge will provide a comprehensive synthesis-structure-property correlation, enabling the rational design of novel solid-state conductors with excellent conductivity and stability.

25 ENERGY STORAGE↗
DOE OSTI2025

Mechanisms and stability of Li dynamics in amorphous Li-Ti-P-S-based mixed ionic–electronic conductors: A machine learning molecular dynamics study

Mixed ionic–electronic conductors (MIECs) exhibit both high ionic and electronic conductivity to improve the battery performance. In this work, we investigate the mechanism and stability of transport channels in our recently developed MIEC material, amorphous Ti-doped lithium phosphorus sulfide (LPS), using molecular dynamics (MD) simulations with a 99% accurate machine-learning force field (MLFF) trained on ab initio MD data. The achieved MLFF helps efficient large-scale MD simulations on LPS with three Ti concentrations (10%, 20%, and 30%) and six temperatures (25°C to 225°C) to calculate ionic conductivity, activation energy, Li-ion transport mechanism, and configurational entropy. Results show that ionic conductivities and activation energies are consistent with our recent experimental values. Moreover, Li-ion transport occurs via free-volume diffusion facilitated by the formation of disordered Li-S polyhedra. The enhanced stability of transport channels at 10% and 20% Ti doping, compared to 0% and 30%, is observed by analyzing the vibrational and configurational entropy of these disordered Li-S polyhedra. Overall, this study highlights the utility of MLFF-based large-scale MD simulations in explaining the transport mechanism and the stability of Li-ion in Ti-doped LPS electrolyte with significant computational efficiency.

And configuration entropy↗
DOE OSTI2026

Probing Interfacial Reaction Pathways in Atomic Layer Deposition on Sulfide Superionic Conductors

Sulfide superionic conductors (e.g., argyrodite Li 6 PS 5 Cl, LPSCl) are extremely promising for all solid-state batteries, but poor atmospheric stability and high interfacial reactivity limit widespread adoption. Coating LPSCl powders with ultrathin coatings using atomic layer deposition (ALD) mitigates these problems, protecting against atmospheric degradation and reducing reactivity with Li metal, yielding more stable cycling. Despite significant promise, the ALD mechanism is unknown, hampering the development of new coating chemistries. In this study, we elucidate the mechanism for Al 2 O 3 ALD on LPSCl using trimethyl aluminum (TMA) and H 2 O by combining in situ Fourier transform infrared spectroscopy, ex situ solid-state magic angle spinning nuclear magnetic resonance, UV Raman spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. We determine that ALD Al 2 O 3 nucleates promptly via TMA reaction with native —OH, —SH, and PS 3 -OH groups to form transient C–Al–O(S) species that are rapidly hydrolyzed during the subsequent H 2 O exposure. This reversible transformation maintains surface nucleophilicity and prevents sulfide decomposition. The resulting layer-by-layer growth leads to highly conformal Al 2 O 3 coatings on LPSCl that are readily scalable to ≥ 50 g quantities using a rotating drum fixture. This detailed understanding of ALD surface reactions provides critical insights guiding the selection of future ALD chemistries with improved performance.

atomic layer deposition↗