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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 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Microstructure Scale Lithium-Ion Battery Modeling: Part I. On Through-Plane Heterogeneity, Impact of Mesh Representation, and Differences between Macro- and Microscale Models

Li-ion battery performance and degradation are strongly correlated with the electrode microstructures and can be modeled at different scales, each with their own limitations. Herein, we compare predictions achieved with a macro- and a micro-scale model, that is, respectively, neglecting or considering the microstructural heterogeneity of the composite electrodes, on virtual numerically generated and real microstructures. While both models are in relative agreement at the low charge rates, differences arise for fast charging scenarios and especially for the real, highly heterogenous, microstructures. The microscale model predicts that electrolyte concentration saturation and depletion, respectively, at the back of the cathode and of the anode are exacerbated, and that lithium plating occurs earlier for real microstructures. The present work also indicates that the mesh representation significantly impacts the microscale model predictions, and consequently that microscale models should add surface area as a parameter to consider explicitly surface roughness. This article is the first of a series, with subsequent entries further investigating in-plane heterogeneities, lithium plating, and the impact of microstructure representativity on model predictions.

25 ENERGY STORAGE↗
DOE OSTI2026

Tailored Solvent Treatment for Optimized Production of Upcycled Anodes from End-Of-Life Li-Ion Batteries

Recycling processes for lithium-ion batteries typically overlook graphite because of its lower market value relative to that of transition-metal-containing cathode materials. However, graphite recovered from cycled lithium-ion batteries holds additional engineered value associated with the solid-electrolyte interphase (SEI). The SEI contributes critical electronic passivation of the graphite surface but becomes highly resistive with extended cycling, yielding poor cell performance. In this work, we apply tailored solvent treatment to end-of-life (EOL) graphite anodes to selectively remove adverse SEI components while retaining beneficially passivating species. We evaluate a series of polar protic solvents to achieve targeted removal of SEI components and control selectivity through rational variation in solvent properties. The physiochemical properties of treatment solvents correlate with both the retained SEI composition and the corresponding electrochemical performance of solvent-treated “upcycled” graphite anodes. Within the initial set of solvents evaluated, top-performing candidates show capacity and Coulombic efficiency nearly equivalent to those of an analogous pristine anode, as well as promising electrochemical performance enhancement with regard to irreversible capacity-loss metrics. This study establishes critical design principles for an optimized anode upcycling method that enhances the value of recycled graphite by retaining and upgrading the SEI.

25 ENERGY STORAGE↗
DOE OSTI2020

Theoretical search for possible Li–Ni–B crystal structures using an adaptive genetic algorithm

The structural diversity of rare-earth and transition metal borides indicates that alkali-transition metal borides (A-T-B) show tremendous promise in exhibiting a variety of crystal structures with different dimensionalities of T-B frameworks. On the other hand, the A-T-B ternary systems are severely underexplored because of the synthetic challenges associated with their preparation. Accurate and efficient computational predictions of low-energy stable and metastable phases can identify the optimal compositions of the hypothetical compounds in the A-T-B systems to guide the synthesis. As such, in this work, we have computationally discovered several new phases in the Li–Ni–B ternary system. The newly discovered LiNiB, Li 2 Ni 3 B, and Li 2 NiB phases expand the existing theoretical database, and the convex-hull surface of Li–Ni–B has been re-constructed. The lowest energy structure of the LiNiB compound has been found by an adaptive genetic algorithm with layered motif, which matches with the experimentally determined structure. According to our electrochemical calculations, LiNiB and another predicted layered Li 2 NiB compounds have great potential as anode materials for lithium batteries. The Li 2 Ni 3 B compound with the space group P4 3 32 was predicted to crystallize in a cubic structure composed of distorted octahedral units of BNi 6 , which is isostructural to two noncentrosymmetric superconductors Li 2 Pd 3 B and Li 2 Pt 3 B. While we were unable to experimentally confirm the Li 2 Ni 3 B compound utilizing the hydride synthetic route, attempts to synthesize this compound by alternate methods remain highly desirable, considering its potential superconducting properties.

36 MATERIALS SCIENCE↗
NASA NTRS2012

Solid State Multinuclear Magnetic Resonance Investigation of Electrolyte Decomposition Products on Lithium Ion Electrodes

Solid electrolyte interphase (SEI) formation in lithium ion cells prepared with advanced electrolytes is investigated by solid state multinuclear (7Li, 19F, 31P) magnetic resonance (NMR) measurements of electrode materials harvested from cycled cells subjected to an accelerated aging protocol. The electrolyte composition is varied to include the addition of fluorinated carbonates and triphenyl phosphate (TPP, a flame retardant). In addition to species associated with LiPF6 decomposition, cathode NMR spectra are characterized by the presence of compounds originating from the TPP additive. Substantial amounts of LiF are observed in the anodes as well as compounds originating from the fluorinated carbonates.

Li-ion battery electrolytes↗
DOE OSTI2021

New Insights into the High‐Performance Black Phosphorus Anode for Lithium‐Ion Batteries

Abstract Black phosphorus (BP) is a promising anode material in lithium‐ion batteries (LIBs) owing to its high electrical conductivity and capacity. However, the huge volume change of BP during cycling induces rapid capacity fading. In addition, the unclear electrochemical mechanism of BP hinders the development of rational designs and preparation of high‐performance BP‐based anodes. Here, a high‐performance nanostructured BP–graphite–carbon nanotubes composite (BP/G/CNTs) synthesized using ball‐milling method is reported. The BP/G/CNTs anode delivers a high initial capacity of 1375 mA h g −1 at 0.15 A g −1 and maintains 1031.7 mA h g −1 after 450 cycles. Excellent high‐rate performance is demonstrated with a capacity of 508.1 mA h g −1 after 3000 cycles at 2 A g −1 . Moreover, for the first time, direct evidence is provided experimentally to present the electrochemical mechanism of BP anodes with three‐step lithiation and delithiation using ex situ X‐ray diffraction (XRD), ex situ X‐ray absorption spectroscopy (XAS), ex situ X‐ray emission spectroscopy, operando XRD, and operando XAS, which reveal the formation of Li 3 P 7 , LiP, and Li 3 P. Furthermore, the study indicates an open‐circuit relaxation effect of the electrode with ex situ and operando XAS analyses.

Li, Minsi↗
DOE OSTI2021

Identification of LiH and nanocrystalline LiF in the solid–electrolyte interphase of lithium metal anodes

A comprehensive understanding of the solid–electrolyte interphase (SEI) composition is crucial to developing high-energy batteries based on lithium metal anodes. A particularly contentious issue concerns the presence of LiH in the SEI. In this work, we report on the use of synchrotron-based X-ray diffraction and pair distribution function analysis to identify and differentiate two elusive components, LiH and LiF, in the SEI of lithium metal anodes. LiH is identified as a component of the SEI in high abundance, and the possibility of its misidentification as LiF in the literature is discussed. LiF in the SEI is found to have different structural features from LiF in the bulk phase, including a larger lattice parameter and a smaller grain size (<3 nm). These characteristics favour Li + transport and explain why an ionic insulator, like LiF, has been found to be a favoured component for the SEI. Finally, pair distribution function analysis reveals key amorphous components in the SEI.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Solvent-Free and Non-Sintered 500 Wh/kg All Solid-State Battery

Navitas teamed up with UMD and ORNL to establish a reliable scientific research team. The project addressed processing limitations of state-of-the-art solid electrolytes by extending solvent-free electrode fabrication technology to the scalable production of cathode/solid electrolyte laminates. The innovation started with a solid-state sulfide electrolyte (LiPS) with Cl stabilization able to meet the keystone conductivity challenge in a film of practical thickness (μ 50 µm). The electrolyte was based on a composite of PTFE, and stabilized LiPSCl. With optimization, the ionic conductivity reached 3.3 ×10 -3 S/cm. The solid electrolyte with as low as 0.4% binder allowed long term cycling (> 500 cycles) of Li/SSE/Li cell at > 4 mA/cm 2 with the utilization of Li > 80%. The Li and SSE interfaces were successfully protected with LiF-rich SEI layer. NCM811cathode active materials were coated with a thin layer of Al 2 O 3 (5 nm). The free standing cathode film was fabricated through dry-process with Al2O3-coated NCM811, LiPSCl, active carbon, and small amount PTFE. The all-solid-state batteries were laminated with free standing surface coated NCM811 cathode film, free standing LiPSCl SSE film, and surface protected Li anode together in a single lamination step, and demonstrated high specific capacity (> 200 mAh/g) with coulombic efficiency > 99.5%. The all-solid-state batteries through solvent-free and no-sintering process are promising for large format cell with 500 Wh/Kg specific energy density.

25 ENERGY STORAGE↗
DOE OSTI2023

Localized high-concentration electrolytes get more localized through micelle-like structures

Liquid electrolytes in batteries are typically treated as macroscopically homogeneous ionic transport media despite having a complex chemical composition and atomistic solvation structures, leaving a knowledge gap of the microstructural characteristics. Here, we reveal a unique micelle-like structure in a localized high-concentration electrolyte, in which the solvent acts as a surfactant between an insoluble salt in a diluent. The miscibility of the solvent with the diluent and simultaneous solubility of the salt results in a micelle-like structure with a smeared interface and an increased salt concentration at the centre of the salt–solvent clusters that extends the salt solubility. These intermingling miscibility effects have temperature dependencies, wherein a typical localized high-concentration electrolyte peaks in localized cluster salt concentration near room temperature and is used to form a stable solid–electrolyte interphase on a Li metal anode. Importantly, these findings serve as a guide to predicting a stable ternary phase diagram and connecting the electrolyte microstructure with electrolyte formulation and formation protocols of solid–electrolyte interphases for enhanced battery cyclability.

25 ENERGY STORAGE↗
DOE OSTI2026

Investigation Into LiCl-LiF+Li 2 O as a Low Temperature Electrolyte in Direct Electrolytic Reduction of UO 2

Direct electrolytic reduction (DER) of UO 2 in a binary LiCl-Li2O (1–3 wt%) at 650 °C has been widely reported. The process temperature can be reduced to 550 °C in theory by using a near eutectic ternary LiCl-LiF+Li 2O (∼2 wt%) electrolyte, which will result in substantial reduction in rate of salt vaporization. The feasibility of using the ternary electrolyte for the process was tested via material compatibility testing, electrochemical polarization testing, and controlled potential or current DER experiments. MgO, Pt, and 625 nickel samples were each contacted with the ternary salt for 168 h. Negligible changes to dimensions and mass of the samples were measured, and concentrations of corrosion products in the salt were 102 ppm or less. O2−oxidation was observed to occur at a lower potential than Cl-or F-on a Pt anode. DER of UO2was performed in six trials. Process variables included type of reference electrode, electrochemical control method, type of cathode basket, and electrolyte composition. UO 2conversion ranged from 28.2 to 99.9 % , and current efficiency ranged from 38 to 52%. Overall, results indicate that the use of the ternary salt is feasible for DER.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Dissolution of the Solid Electrolyte Interphase and Its Effects on Lithium Metal Anode Cyclability

At >95% Coulombic efficiencies, most of the capacity loss for Li metal anodes (LMAs) is through the formation and growth of the solid electrolyte interphase (SEI). However, the mechanism through which this happens remains unclear. One property of the SEI that directly affects its formation and growth is the SEI’s solubility in the electrolyte. Here, in this work, we systematically quantify and compare the solubility of SEIs derived from ether-based electrolytes optimized for LMAs using in-operando electrochemical quartz crystal microbalance (EQCM). A correlation among solubility, passivity, and cyclability established in this work reveals that SEI dissolution is a major contributor to the differences in passivity and electrochemical performance among battery electrolytes. Together with our EQCM, X-ray photoelectron spectroscopy (XPS), and nuclear magnetic resonance (NMR) spectroscopy results, we show that solubility depends on not only the SEI’s composition but also the properties of the electrolyte. This provides a crucial piece of information that could help minimize capacity loss due to SEI formation and growth during battery cycling and aging.

25 ENERGY STORAGE↗
DOE OSTI2020

Perspectives on the relationship between materials chemistry and roll-to-roll electrode manufacturing for high-energy lithium-ion batteries

As lithium-ion battery (LIB) active material and cell manufacturing costs continue to drop with wider adoption of electric vehicles, electrode and cell processing costs remain too high in terms of reaching the ultimate U.S. Department of Energy (DOE) cell cost target of $80/kWh. This paper primarily covers major materials chemistry advancements made over the last 10 years at Oak Ridge National Laboratory (ORNL) in the space of advanced manufacturing science for LIBs with the aim of simultaneously meeting the ultimate cost target, 500 Wh/kg gravimetric energy density, 10-15-min fast charge times, and 1000 deep discharge cycles. Aqeous electrode processing with a variety of active anode and cathode materials is now a standard procedure at the DOE Battery Manufacturing R&D Facility at ORNL (BMF), including the latest processes developed for Ni-rich cathodes. New results on cobalt-free LiNi 0.8 Fe 0.1 Al 0.1 O 2 (NFA 811) are also included and discussed in an electrode processing advantage context. In addition, colloidal processing advancements have been made for Si/C composite anodes for achieving >600 mA h/g capacities. Optimization of electrode coating parameters and drying protocols have been completed, which has elucidated how key processing variables need to be changed when parameters such as slurry solids loading, solvent type, and wet electrode thickness are changed. ORNL has also increased the line speeds at which thick cathodes can be processed using ultra-fast electron beam (EB) curing and substantially decreased formation cycling times to <1 day. Finally, key details of these advancements are discussed in the context of materials chemistry and process-property-performance relationships.

25 ENERGY STORAGE↗
DOE OSTI2020

Hierarchical porous silicon structures with extraordinary mechanical strength as high-performance lithium-ion battery anodes

Abstract Porous structured silicon has been regarded as a promising candidate to overcome pulverization of silicon-based anodes. However, poor mechanical strength of these porous particles has limited their volumetric energy density towards practical applications. Here we design and synthesize hierarchical carbon-nanotube@silicon@carbon microspheres with both high porosity and extraordinary mechanical strength (>200 MPa) and a low apparent particle expansion of ~40% upon full lithiation. The composite electrodes of carbon-nanotube@silicon@carbon-graphite with a practical loading (3 mAh cm −2 ) deliver ~750 mAh g −1 specific capacity, <20% initial swelling at 100% state-of-charge, and ~92% capacity retention over 500 cycles. Calendered electrodes achieve ~980 mAh cm −3 volumetric capacity density and <50% end-of-life swell after 120 cycles. Full cells with LiNi 1/3 Mn 1/3 Co 1/3 O 2 cathodes demonstrate >92% capacity retention over 500 cycles. This work is a leap in silicon anode development and provides insights into the design of electrode materials for other batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Compositions and Formation Mechanisms of Solid-Electrolyte Interphase on Microporous Carbon/Sulfur Cathodes

We report the formation mechanism and compositions of a solid-electrolyte interphase (SEI) on a microporous carbon/sulfur (MC/S) cathode in Li–S batteries using a carbonate-based electrolyte (1 M LiPF 6 in ethylene carbonate (EC)/dimethyl carbonate, v:v = 1:1). Through characterizations using 1D and 2D solution-phase nuclear magnetic resonance spectroscopy, coupled with model chemical reactions and DFT calculations, we have identified two critical roles of Li + in steering the SEI formation. First, the preferential solvation of Li + by EC in the mixed carbonate electrolyte renders EC as the dominant participant in the SEI formation, and second, Li + coordination to the EC carbonyl alters activation barriers and changes the reaction pathways relative to Na + . The main organic components in the SEI are identified as lithium ethylene monocarbonate and lithium methyl carbonate, which are virtually identical to those formed on Li and graphite anodes of lithium-ion batteries but via a different pathway.

25 ENERGY STORAGE↗
DOE OSTI2024

Mechanochemically Enabled Metastable Niobium Tungsten Oxides

Metastable compounds have greatly expanded the synthesizable compositions of solid-state materials and have attracted enormous amounts of attention in recent years. Especially, mechanochemically enabled metastable materials synthesis has been very successful in realizing cation-disordered materials with highly simple crystal structures, such as rock salts. Application of the same strategy for other structural types, especially for non-close-packed structures, is peculiarly underexplored. Niobium tungsten oxides (NbWOs), a class of materials that have been under the spotlight because of their diverse structural varieties and promising electrochemical and thermoelectric properties, are ideally suited to fill such a knowledge gap. In this work, we develop a new series of metastable NbWOs and realize one with a fully cation-disordered structure. Furthermore, we find that metastable NbWOs transform to a cation-disordered cubic structure when applied as a Li-ion battery anode, highlighting an intriguing non-close-packed–close-packed conversion process, as evidenced in various physicochemical characterizations, in terms of diffraction, electronic, and vibrational structures. Lastly, by comparing the cation-disordered NbWO with other trending cation-disordered oxides, we raise a few key structural features for cation disorder and suggest a few possible research opportunities for this field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Structure and lithium insertion in oxides of molybdenum

Oxides of molybdenum, MoO x , have a rich structural chemistry arising from the accommodation of oxygen deficiency as MoO 3 is reduced and varied redox behavior arising from the ability of Mo to take on several different oxidation states. We review MoO 3 , MoO 2 , and all the reduced Mo oxides with intermediate compositions for their performance as Li-ion battery electrode materials. These reduced oxides are perhaps the most structurally diverse in the field of energy storage materials, taking on structures ranging from ones with crystallographic shear to bronze-like structures and distorted rutile. The crystal structure can have a significant impact on the performance of battery materials, which makes the reduced Mo oxides a promising domain of study. Electrochemical studies of these oxides from as early as 1971 to as recently as 2022 are compiled, and characteristics of capacity, capacity retention, and rate performance are compared. We find that certain oxides indeed display promising and highly reversible capacities for Li + storage. Typical redox voltages for Mo oxides lie in a regime that hinders maximizing energy density when they are paired with higher-voltage cathodes or lower-voltage anodes. The possibility of decreasing the redox voltage in the future will expand the promise of these materials while offering an alternative to more critical elements such as Nb.

25 ENERGY STORAGE↗
DOE OSTI2024

Recent Progress on Dominant Sulfide‐Type Solid‐State Na Superionic Conductors for Solid‐State Sodium Batteries

Abstract Over the past decade, solid‐state batteries have garnered significant attentions due to their potentials to deliver high energy density and excellent safety. Considering the abundant sodium (Na) resources in contrast to lithium (Li), the development of sodium‐based batteries has become increasingly appealing. Sulfide‐based superionic conductors are widely considered as promising solid eletcrolytes (SEs) in solid‐state Na batteries due to the features of high ionic conductivity and cold‐press densification. In recent years, tremendous efforts have been made to investigate sulfide‐based Na‐ion conductors on their synthesis, compositions, conductivity, and the feasibility in batteries. However, there are still several challenges to overcome for their practical applications in high performance solid‐state Na batteries. This article provides a comprehensive update on the synthesis, structure, and properties of three dominant sulfide‐based Na‐ion conductors (Na 3 PS 4 , Na 3 SbS 4 , and Na 11 Sn 2 PS 12 ), and their families that have a variety of anion and cation doping. Additionally, the interface stability of these sulfide electrolytes toward the anode is reviewed, as well as the electrochemical performance of solid‐state Na batteries based on different types of cathode materials (metal sulfides, oxides, and organics). Finally, the perspective and outlook for the development and practical utilization of sulfide‐based SE in solid‐state batteries are discussed.

Guo, Xiaolin↗
DOE OSTI2020

A chemically stabilized sulfur cathode for lean electrolyte lithium sulfur batteries

Lithium sulfur batteries (LSBs) are promising next-generation rechargeable batteries due to the high gravimetric energy, low cost, abundance, nontoxicity, and high sustainability of sulfur. However, the dissolution of high-order polysulfide in electrolytes and low Coulombic efficiency of Li anode require excess electrolytes and Li metal, which significantly reduce the energy density of LSBs. Quasi-solid-state LSBs, where sulfur is encapsulated in the micropores of carbon matrix and sealed by solid electrolyte interphase, can operate under lean electrolyte conditions, but a low sulfur loading in carbon matrix (<40 wt %) and low sulfur unitization (<70%) still limit the energy density in a cell level. Here, we significantly increase the sulfur loading in carbon to 60 wt % and sulfur utilization to ∼87% by dispersing sulfur in an oxygen-rich dense carbon host at a molecular level through strong chemical interactions of C–S and O–S. In an all-fluorinated organic lean electrolyte, the C/S cathode experiences a solid-state lithiation/delithiation reaction after the formation of solid electrolyte interphase in the first deep lithiation, completely avoiding the shuttle reaction. The chemically stabilized C/S composite retains a high reversible capacity of 541 mAh⋅g −1 (based on the total weight of the C/S composite) for 200 cycles under lean electrolyte conditions, corresponding to a high energy density of 974 Wh⋅kg −1 . The superior electrochemical performance of the chemical bonding-stabilized C/S composite renders it a promising cathode material for high-energy and long-cycle-life LSBs.

25 ENERGY STORAGE↗
DOE OSTI2026

Impact of Fermentation-Derived Substrates on Hydrogen Production in Zero-Gap Microbial Electrolysis Cells

Zero-gap microbial electrolysis cells (MECs) represent a promising platform for hydrogen production from liquid waste streams due to reduced interelectrode spacing that lowers internal resistance and enhances mass transport. However, the performance and stability of zero-gap MECs treating chemically complex feedstocks remain insufficiently characterized. Here, we operated zero-gap MECs with real, unamended, corn stover dark fermentation effluent containing a wide range of organic substrates. The MECs fed fermentation effluent achieved a maximum current density of 24 A/m2 (15+-6 A/m2 over the cycle) and a hydrogen production rate of 75 L/L-d (42+-19 L/L-d over the cycle). The substrates were consumed at different rates, indicating substrate-selective utilization by the anodic microbial community. Acetate supported high and stable current generation, whereas ethanol, formate, lactate, and amino acids induced varying degrees of inhibition depending on their concentration. Residual sugars caused pronounced current fluctuations, consistent with ongoing fermentation and local pH changes. A diverse microbial community was crucial for efficiently utilizing complex organics and maximizing electrochemical performance. These results demonstrate how and to what extent substrate composition regulates zero-gap MEC performance and that microbial community and operational conditions can be leveraged to enhance performance. These novel findings provide practical guidance for achieving robust hydrogen recovery from chemically heterogeneous real liquid waste streams.

08 HYDROGEN↗