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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Single-Crystallization of O3-Type Layered Oxide Cathode for Na-Ion Battery

The development of high-energy-density Na-ion batteries places significant demands on single-crystal layered oxide cathodes, especially for further high-voltage, solid-state battery scenarios. In the O3-type structure, due to the original sluggish Na ion diffusion kinetics (approximately 1 order of magnitude lower than that of Li-ion), and further hindrance against diffusion kinetics caused by single-crystal architecture, these inherent defects lead to the decline in the electrochemical performance. Herein, we demonstrated that the single crystallization of O3-type NaNi 1/3 Fe 1/3 Mn 1/3 O 2 cathode (d 50 = 5.04 μm) aggravates surface-to-bulk phase inhomogeneity distribution, which is attributed to the uneven Na ions extraction. Moreover, the Na-depletion of the surface/shell region not only aggravates Na ion diffusion resistance but also leads to a higher valence state of transition-metal elements (e.g., Ni/Fe) near the surface of the single-crystal particle, which further compromises the cathode-electrolyte interface stability. Furthermore, not limited to revealing the challenges, tuning the particle size and moderating quasi-single-crystal strategies have been proven to effectively mitigate the negative uneven distributions of Na ions, phases, and valence/oxidative states, resulting in efficient modification for single crystallization of Na-layered oxide cathodes.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Electrochemical Oxidation in Garnet-Type Solid Electrolyte by Formation of Point Defects

All-solid-state batteries hold greater promise for improving safety and energy density over conventional battery technology employing organic liquid electrolytes. One of the required features of a Li + conducting solid electrolyte is electrochemical stability, attained thermodynamically or kinetically, within the targeted operating voltage and temperature ranges. Therefore, understanding of the oxidative or reductive degradation mechanism is important to allow the design of stable solid electrolyte materials. This work contributes to building an understanding of the oxidative degradation mechanism in lithium solid electrolytes at cell operating conditions. Here, we have focused on resolving the oxidative decomposition mechanism of Al-doped lithium garnet Li 6.28 Al 0.24 La 3 Zr 2 O 12 (LLZO) as a state-of-the-art inorganic ceramic electrolyte. By combining experimental and computational analyses, we show that oxidation of LLZO occurs by simultaneous loss of oxygen and lithium from the structure, resulting in substoichiometric LLZO, at a moderate temperature (80 °C) and a high electrode potential (4.3 V vs Li/Li + ). Based on X-ray absorption and diffraction analyses, we find that the zirconium coordination shells in LLZO contract while the crystal structure experiences positive chemical strain upon electrochemical oxidation. The results from ex situ structural characterization of both the local structure and crystal symmetry are supported by a substoichiometric LLZO with lithium and oxygen vacancies, modeled by density functional theory (DFT) calculations. These chemical and structural changes in LLZO suppress effective lithium-ion conductivity by an order of magnitude. Formation of lithium and oxygen vacancies in LLZO upon electrochemical oxidation is different from prior thermodynamic predictions of phase decomposition of LLZO. The difference here is that the experiments were conducted at near-room temperature, which can hinder the kinetics of phase separation, and thus, the resultant LLZO solid electrolyte is still single-phase but substoichiometric in Li and O. In conclusion, these findings contribute an important degradation mechanism of the electrolyte, relevant for practical operational conditions of solid-state batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Ultrafast Sintering and Dopant Effects in Garnet LLZO Solid Electrolytes

High-throughput, low-cost manufacturing, and optimization of solid electrolytes are necessary for the adoption of solid-state batteries. In this work, garnet-type Li 7 La 3 Zr 2 O 12 (LLZO) with different aliovalent dopants, 𝑇𝑎$_{^·_{𝑍𝑟}}$, 𝐴𝑙$^{··}_{𝐿𝑖}$, and 𝐺𝑎$^{··}_{𝐿𝑖}$, have been ultrafast-sintered with different temperature ramping rates. The densification behavior, phases, their evolution, and surface chemistry of different LLZO have been investigated and linked to their electrochemical performances. It has been shown that LLZO with 𝑇𝑎$_{^·_{𝑍𝑟}}$ dopant demonstrates the highest garnet phase purity and overall best electrochemical performances, and ultrafast sintering further improves densification, ionic conductivity, and electrochemical stability. On the other hand, LLZO doped with 𝐴𝑙$^{··}_{𝐿𝑖}$ and 𝐺𝑎$^{··}_{𝐿𝑖}$ are reaching higher cubic phase purities and ionic conductivities via conventional sintering, indicating undesirable dopant migration and segregation during the ultrafast sintering process. In conclusion, these findings provide insights into the manufacturing of solid electrolyte materials.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Complex Dynamics in Argyrodite Solid-State Ion Conductors

Argyrodites are a compositionally diverse family of materials that exhibit remarkable ion transport properties. While the average crystal structures of argyrodites have been extensively studied, ion transport in these materials is governed by a confluence of dynamic processes spanning the cation, anion, and polyanionic sublattices. This Perspective synthesizes recent advances in understanding the role of dynamics in structural behavior and ion transport properties. We examine the compositional and structural motifs that govern order−disorder transitions within the argyrodite family and further explore how ion hopping is facilitated by lattice dynamics, from long-range phonons to local rotational dynamics of polyanionic species. Through the lens of dynamics spanning multiple time and length scales, we establish guiding principles that govern transport phenomena and highlight avenues of future study for the argyrodite family of ion conductors.

36 MATERIALS SCIENCE↗
DOE OSTI2025

The Influence of Charge Correlation and Ion Solvation on the Phase Behavior of Single-Ion Conducting Polymer Blend Electrolytes Using SAXS/SANS

Single-ion conducting polymer blends (SICPBs) have demonstrated exceptional electrochemical performance as solid-state battery electrolytes; however, their nanoscale morphology and thermodynamic behavior remain unexplored. In this work, we investigate blends composed of deuterated poly(ethylene oxide) and poly[lithium sulfonyl(trifluoromethane sulfonyl)imide methacrylate], dPEO/P(LiMTFSI), and report the first experimental study of the nanostructures of charge-neutral polymer blends using small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS). Despite the macroscopic miscibility indicated by a single glass-transition temperature, SANS and SAXS results reveal disordered, charge-correlated nanostructures that are strongly influenced by blend composition and temperature. At low concentrations of charge polymer, the scattering is dominated by concentration fluctuations, and the random phase approximation is applied to extract values of the Flory–Huggins interaction parameter, χ SC . At higher charged polymer content, concentration fluctuations are suppressed, and a correlation model is used to characterize the nanostructures of the charge correlations. We find that the structures of the charge correlations are highly dependent on blend composition─consistent with predictions from Sing’s self-consistent field theory-liquid state models. Understanding these features is essential for uncovering the ion transport mechanism that leads to improved electrochemical performance previously reported in SICPB systems.

25 ENERGY STORAGE↗
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 OSTI2025

Revisiting the Role of Mobile Ion Size for the Activation Barrier of Charge Transport in Single Ion Conducting Polymers

The development of polymer electrolytes for energy storage and conversion technologies requires a fundamental understanding of the material parameters controlling the energy barriers for ion transport. In glassy polymers, these activation barriers are usually extracted by using Arrhenius procedures. However, our recent studies of single ion conducting polymers reveal that this traditional Arrhenius description provides anomalously small prefactors, an issue that is widely disregarded in the literature. Here, to address it, an alternative approach was introduced for extracting the effective activation barrier E by imposing a physically valid limit (∼10 –13 s) for the ion hopping attempt time. Two consequences of this recent approach are that in polymer electrolytes (i) E is significantly (∼30–40%) lower than the barrier estimated using traditional Arrhenius fits and (ii) E displays significant temperature dependence even in the glassy state. Under these circumstances, we are revisiting the role of ion size, glass transition temperature T g , and dielectric and elastic constants of the polymer matrix on the effective activation barriers for ion transport as extracted using the recently proposed approach and highlight the differences from the picture that previously emerged based on simplistic apparent Arrhenius analysis. To this end, we investigate cation transport in three families of single ion conducting trifluoromethane sulfonimide-based polyanions with varied T g . Our results indicate that E decreases with mobile cation size and is highly sensitive to changes in the dielectric permittivity of the matrix, even for large cations. These insights call for revisions of many earlier results based on apparent Arrhenius fits as the proposed approach can provide more accurate guidance for the design of polymer electrolytes with enhanced ionic conductivity.

energy barrier↗
DOE OSTI2025

Nanoporous Fe 2 O 3 and Soluble Fe(II) Intermediates Accelerate the Electrodeposition of Fe in NaOH(aq)

Electrochemical conversion of iron oxide to iron metal can enable low-cost batteries for long duration energy storage and zero-emissions ironmaking for steel. Iron oxides, such as hematite, can be electrochemically reduced to metallic iron in concentrated alkaline electrolytes at modest temperatures, but the relative influences of solid-state and dissolved intermediates at practical reaction rates remains unclear. Here, in this study, we prepare a homologous set of well-defined hematite particles to measure how the nanoscale morphology of oxides controls both their reactivity and apparent reduction mechanism in concentrated hydroxide. Correlated electron microscopy and rotating-ring-disk-electrode measurements revealed that nanoporous hematite and solid intermediates formed iron via a dissolution-redeposition pathway. In contrast, dense hematite particles directly formed iron metal via reactive fracture. While previous studies on iron electrowinning have primarily emphasized the role of particle diameter at the micron scale, these results demonstrate the importance of the dissolution-redeposition pathway to support rapid reaction rates and suggest that nanoscale porosity controls iron oxide reactivity at temperatures <100 °C. Therefore, iron-oxide-to-metal electrolyzers and fast-charging iron-air batteries supported by curtailed electricity can increase the rate of metal formation by accelerating fracture and dissolution in reactant oxides.

TEM↗
DOE OSTI2026

Elimination of detrimental grain boundary segregation in garnets

Garnet Li 7 La 3 Zr 2 O 12 electrolyte is considered a key enabler of solid-state batteries with Li metal electrodes, but the grain boundaries impair its performance. To date, the understanding of grain boundary structures and its impact on performance remains elusive. Here, we show that element segregation at Li 7 La 3 Zr 2 O 12 grain boundaries critically governs Li transport and nucleation. During conventional sintering, Al, Ta, and La segregate at grain boundaries, locally depleting Li and creating space-charge layers that lower total ionic conductivity. Simultaneously, this segregation leads to higher electronic conductivity along grain boundaries, which promotes Li nucleation at grain boundary edges with increased risk of dendrite formation. The underlying mechanism of segregation is governed by both thermodynamic driving forces and diffusion kinetics. Building on this understanding, we develop a strategy to achieve segregation-free grain boundaries through a rapid sintering protocol that utilizes the onset of solid-state softening. This approach yields transparent, polycrystalline Li 7 La 3 Zr 2 O 12 with negligible grain boundary impedance and enhanced dendrite tolerance. By elucidating the structural origins and electrochemical consequences of grain boundary segregation, this work provides a guidance for the rational optimization of solid electrolytes.

Energy - Storage↗
DOE OSTI2025

Five-volt-class high-capacity all-solid-state lithium batteries

Advances in battery technology have been impeded by the voltage constraints of electrolytes. Here, in this study, we present a high-energy all-solid-state battery design featuring >5 V operation and an ultrahigh areal capacity of 35.3 mAh cm −2 ; these attributes were enabled by a highly conductive and ultrahigh-voltage stable fluoride solid electrolyte, LiCl–4Li 2 TiF 6 (1.7 × 10 −5 S cm −1 at 30 °C). LiCl–4Li 2 TiF 6 shields high-voltage spinel oxide cathodes, achieving 106 mAh g −1 at 2C with 75.2% retention over 500 cycles for LiNi 0.5 Mn 1.5 O 4 , sharply contrasting with the conventional LiNbO 3 counterpart, which decomposes and fails to prevent detrimental interfacial degradation. The efficacy of LiCl–4Li 2 TiF 6 is validated across various systems, including LiCoMnO 4 , LiFe 0.5 Mn 1.5 O 4 and pouch-type LiNi 0.5 Mn 1.5 O 4 ||Li (or Ag–C) all-solid-state batteries, and further demonstrated by operability down to 2.3 V with 258 mAh g −1 and ultrathick 1.8-mm electrodes. This shielding layer with >5 V stability introduces a transformative design paradigm by revisiting the previously forbidden high-voltage cathodes.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Heterogeneous doping via nanoscale coating impacts the mechanics of Li intrusion in brittle solid electrolytes

Lithium dendrite intrusion in solid-state batteries limits fast charging and causes short-circuiting, yet the underlying regulating mechanisms are not well-understood. Here, in this work, we discover that heterogeneous Ag + doping dramatically affects lithium intrusion into Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 (LLZO), a brittle solid electrolyte. Nanoscale Ag + doping is achieved by thermally annealing a 3-nm-thick metallic coating on LLZO, inducing Ag–Li ion exchange and Ag diffusion into grains and grain boundaries. Density functional theory calculations and experimental characterization show negligible impact on the electronic properties and surface wettability from Ag + incorporation. Mechanically, nanoindentation experiments show a fivefold increase in the mechanical force required to fracture the surface Ag + -doped LLZO, indicating substantial doping-induced surface toughening. Operando microprobe scanning electron microscopy experiments show that the Ag + -doped LLZO surface exhibits improved lithium plating at >250 mA cm −2 and an electroplating diameter that is expanded by over fourfold, even under an extreme indentation stress of 3 GPa. This demonstrates enhanced defect tolerance in LLZO, rather than electronic or adhesion effects. Our study reveals a chemo-mechanical mechanism via surface heterogeneous doping, complementing present bulk design rules to minimize mechanical failures in solid-state batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Phase instability-coupled fracture behavior in garnet LLZO solid electrolytes: a machine learning-enabled atomistic study

Fracture in the garnet-type solid electrolyte Li 7 La 3 Zr 2 O 12 (LLZO) poses a critical threat to both the performance and safety of solid-state batteries. To unravel the coupled chemomechanical processes that govern fracture in LLZO under external loading, we carry out large-scale molecular-dynamics simulations with a validated machine-learning force field. Our results demonstrate that triaxial stresses at crack flanks trigger a localized cubic-to-tetragonal phase transformation, which is accompanied by Li-ion rearrangement. The emergent tetragonal domains feature lattice contraction normal to the fracture plane, imposing coherent misfit strains that provide an additional driving force for further crack propagation. Crucially, introducing Li deficiencies stabilizes the cubic phase, postponing the phase transition and thereby delaying fracture initiation. These findings highlight the role of intrinsic phase instability in dictating LLZO's fracture resistance and its critical connection to local Li concentration. This chemomechanical coupling points toward targeted strategies to enhance the mechanical robustness of garnet electrolytes, including tuning Li content, ensuring dopant homogeneity, and refining processing protocols.

Materials science↗
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↗
NASA NTRSDate not supplied

Lithium Nucleation of Anode-Free Solid-State Batteries with a Dry Compressible Interlayer

Anode-free lithium batteries offer promising advantages, including increased energy density and the ability to address common mechanistic failures within the cell, thus increasing safety. One way that can make this possible is to control lithium nucleation. This could be achieved by reducing the overpotential required and implanting lithophilic nucleation sites in an anodic interlayer to aid in lithium ion transport and plating. The concept has been utilized in solid-state battery systems where electrolytes are solids with further improved safety and structural longevity. In this presentation, we discuss the use of a silver-holey graphene-based anodic interlayer that can be fabricated via direct dry compression without the use of solvent or binder. The addition of silver to the holey graphene matrix creates a route to lithium plating via a lower-energy intermediate. This idea is supported by the presence of a lithium-silver alloy that forms during the activation step. It is understood that the embedded silver acts as a nucleation site for lithium ions, thereby assisting in even plating. This control, combined with the added cushion of the holey graphene itself, can help reduce dendrite formation, ultimately increasing the safety and lifetime of the solid-state batteries.

Solid state batteries↗