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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

The Linkage Between Electro-Chemical Mechanical Instabilities in Battery Materials

Battery chemistry must be diversified to achieve a sustainable energy landscape by effectively utilizing renewable energy sources. Alkali metal-ion, all-solid-state, metal–air batteries, and multivalent batteries offer unique cost, safety, raw material abundance, energy, and power density solutions. However, realizing these “beyond Li-ion batteries” must uncover their working principles and performance & property relationships. In this aspect, mitigating chemo-mechanical instabilities in the structure and surface of the electrodes plays a crucial role in their performance. Unfortunately, the coupling between electrochemical and mechanical interactions is often poorly understood due to a lack of operando characterization. Here, this review article explains the working principles of curvature measurement and digital image correlation for measuring stress and strain generations in battery materials. We provided specific examples of how these operando mechanical measurements shed light on instabilities in alkali metal ion electrodes, solid electrolytes, Li-O 2 batteries, and aqueous Zn-ion batteries. Operando mechanical measurements offer an effective way to map changes in the physical fingerprint of the battery materials, therefore providing crucial information to elucidate instabilities in battery materials.

25 ENERGY STORAGE↗
DOE OSTI2024

Highly disordered amorphous Li-battery electrolytes

"Medium-entropy" highly disordered amorphous Li garnets, with ≥4 unique local bonding units (LBUs), hold promise for use as solid-state electrolytes in hybrid or all-solid-state batteries owing to their grain-boundary-free nature and low-temperature synthesis requirement. Through this work, we resolved the local structure of amorphous Li garnet and understood their implication for Li dynamics. These medium-entropy amorphous structures possess unique characteristics with edge- and face-sharing LBUs, not conforming to the classic Zachariasen glass formation rules, and can be synthesized in a wide but processing-friendly temperature range (<680°C). Within these amorphous structures, Li and Zr are identified as the network formers and La as network modifier, with maxima in Li dynamics observed for smaller Li-O and Zr-O coordination; this structure understanding serves as a baseline for identifying additional network formers to further modulate Li transport. In conclusion, our insight provides fundamental guidelines for the structure and phase design for amorphous Li garnets and paves the way for their integration in next-generation batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Synchrotron small-angle X-ray scattering technique for battery electrode study

Structure dependent stability is a concern for the achievement of high energy density electrode with long cycling lifetime, especially for alloying-type and conversion-type anodes. Substantial alterations in volume upon discharge-discharge process leads to particle pulverization and continuous consumption of electrolyte. Moreover, the nucleation and growth mechanism of Li 2 O and Li 2 S, which determines the rate performance of Li-O 2 and Li-S batteries, are still understudy. Microstructure characterization techniques have been applied to disclose the structural changes of active material at different charge/discharge states. Synchrotron small-angle X-ray scattering (SAXS) attracts considerable attention because of the high flux, high time resolution and nondestructive characteristics. In addition, SAXS patterns provide statistics structural information of electrode at micrometer scale. The commonly used coin cell with punched holes simplifies the application of in situ/operando SAXS measurement. Here, this review discusses the research about the SAXS technique in the characterization of electrode in different batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

The role of Li doping in layered/layered Na x Li y Ni 0.4 Fe 0.2 Mn 0.4 O 2 intergrowth electrodes for sodium ion batteries

Here, the layered NaTMO 2 (TM = Ni, Fe, Mn) materials with the O3-type structure are attractive as positive electrodes for sodium ion batteries because of their high theoretical capacity. Additionally, Li doping in these materials has been shown to offer substantial enhancements to their electrochemical properties by promoting the formation of intergrowth structures, which are combinations of specific phases. However, the mechanism by which the intergrowth modifies the electrochemical properties is often unclear. Systematic variation of Li content in Na x Li y Ni 0.4 Fe 0.2 Mn 0.4 O 2 (NFM-Li y ) was conducted to identify its role in structural modification and electrochemical performance. Li contents of 0.15 and greater generate a layered/layered Na-O3/Li-O’3 intergrowth structure. 7 Li and 23 Na nuclear magnetic resonance and x-ray absorption spectroscopy identify that when the total solubility for alkali ions in the layered structure is exceeded, Li continues to form the Li-O’3 phase while the excess Na forms residual sodium compounds such as Na 2 O. Higher Li content is associated with improved capacity retention in the initial cycles from the superior stability of the mechanically linked NaO3/Li-O’3 structure that suppresses the P3 to OP2 phase transition during charge. However, high Li contents are associated with increased rates of parasitic side reactions that reduce long-term cycling stability. These side reactions are associated with the instability of the cathode-electrolyte interphase, which can be partially mitigated by atomic layer deposition (ALD) coating with alumina, which significantly enhances the capacity retention and Coulombic efficiency over many cycles. Overall, we find that the layered/layered Na-O3/Li-O’3 intergrowth structure is able to provide structural stability and suppress undesired phase transformations but is overwhelmed by the increased reactivity of the surface if not protected by surface coating.

25 ENERGY STORAGE↗
DOE OSTI2020

Computational study of the adsorption of bimetallic clusters on alumina substrate

We performed computational investigation of the adsorption of bimetallic Pd 3 M 2 (where M changes from Ag, Au, Co, Cu, Mn, Ni, Pt, and Ru) cluster on the hydroxylated alumina surface. Previously, it was shown that small silver cluster can control the rate of discharge at the cathode of lithium-oxygen battery. The gap near the fermi energy was shown to control the oxygen reduction, an important reaction for LiO 2 formation. Controlling the gap would ultimately control the rate of LiO 2 formation. One can vary the size of the cluster to vary the gap, however, this "knob" provides limited variance in the gap. Alloying, in combination with size variation offer a much wider control of the gap, hence the LiO 2 formation. Using Density Functional Theory (DFT), we determined the most stable geometry of the bimetallic clusters Pd 3 M 2 and calculated the binding energies of these clusters on the alumina substrate which ranges from 0.2 eV to 0.25 eV depending upon the composition of the alloy-cluster, its orientation and the adsorption site. We also find that Pd atoms bind strongly with the substrate oxygen atoms with an average short bond-length of about 2.2 angstrom. We explored how the gap at the Fermi level of the system varies as a function of elemental composition and the calculated gap ranges from 0 meV to 90 meV. Charges distribution using Bader analysis was also performed to probe how charges are transferred between the cluster and the substrate. These preliminary results will open the door for more systematic studies of alloy clusters of different size and stoichiometry for Li-O 2 battery cathode design.

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

Chemical factors controlling the behaviour of oxide cathodes in batteries

Oxide cathodes enable high-energy lithium-ion and sodium-ion batteries, with their performances fundamentally governed by three interrelated chemical factors: electronic configuration, chemical bonding, and chemical reactivity. Here, we illustrate how these factors dictate the redox energy, structural stability, ionic and electronic transport, and interfacial behavior in both layered oxide and polyanion oxide cathodes. We discuss how crystal-field effects and octahedral-site stabilization energies influence cation migration, and how inductive effects tune bond covalency and operating voltages. We also explain how chemical bonding governs thermal stability, gas evolution, and first-cycle capacity loss, and how alignment of transition-metal redox band with the oxygen 2p band determines electrolyte reactivity. Comparison between lithium and sodium layered oxides further reveals how differences in Li-O and Na-O bond ionicity affect chemical reactivity. Finally, we outline strategies including compositional tuning, surface doping, and electrolyte optimization, and emphasize how high-throughput, data-driven approaches in guiding the design of next-generation oxide cathodes.

25 ENERGY STORAGE↗
NASA NTRS1989

Age hardening characteristics and mechanical behavior of Al-Cu-Li-Zr-In alloys

An investigation was conducted to determine the age-hardening response and cryogenic mechanical properties of superplastic Al-Cu-Li-Zr-In alloys. Two alloys with compositions Al-2.65Cu-2.17Li-O.13Zr (baseline) and Al-2.60Cu-2.34Li-0.16Zr-0.17In were scaled-up from 30 lb permanent mold ingots to 350 lb DC (direct chill) ingots and thermomechanically processed to 3.2 mm thick sheet. The microstructure of material which contained the indium addition was partially recrystallized compared to the baseline suggesting that indium may influence recrystallization behavior. The indium-modified alloy exhibited superior hardness and strength compared to the baseline alloy when solution-heat-treated at 555 C and aged at 160 C or 190 C. For each alloy, strength increased and toughness was unchanged or decreased when tested at - 185 C compared to ambient temperature. By using optimized heat treatments, the indium-modified alloy exhibited strength levels approaching those of the baseline alloy without deformation prior to aging. The increase in strength of these alloys in the T6 condition make them particularly attractive for superplastic forming applications where post-SPF parts cannot be cold deformed to increase strength.

Wagner, John A.↗
DOE OSTI2021

Enhancing the performance of lithium oxygen batteries through combining redox mediating salts with a lithium protecting salt

Li–O 2 batteries have recently emerged to meet nowadays elevated electric energy demands. Redox mediators (RMs) for solution-inducing decomposition of discharge products are one approach to increase energy efficiency and reduce high overpotentials in these batteries. However, multiple obstacles hinder their usage such as redox shuttling, capacity fading, electrolyte degradation, etc. Herein, we present a new chemistry based on a combination of LiNO 3 , TEGDME and an ionic liquid that enables LiI (1 M) to lower the charge potential (3.5V) with a long cycle life of 270 cycles. 0.1 M LiI increases the cyclability up to 500 with a slightly increased charge potential (~4V) for a fixed capacity of 1000 mAh/g. Up to 100 cycles, this battery system retained ~95% Li 2 O 2 capacity with a ~0.8 V charge-discharge polarization gap. The addition of LiNO 3 to the electrolyte provides a protective solid electrolyte interface (SEI) on anode that works in synergy with the LiI RM. Moreover, we found that this electrolyte blend results in domain formation of ionic and neutral species enhancing the discharge and charge processes. Finally, DFT calculations provide a better understanding of the role of the anode SEI layer and the Li 2 O 2 decomposition promoted by the LiI during charge on the cathode.

25 ENERGY STORAGE↗
DOE OSTI2021

High-Rate Long Cycle-Life Li-Air Battery Aided by Bifunctional InX3 (X = I and Br) Redox Mediators

Redox mediators (RMs) are solution-based additives that have been extensively used to reduce the charge potential and increase the energy efficiency of Li–oxygen (Li–O 2 ) batteries. However, in the presence of RMs, achieving a long cycle-life operation of Li–O 2 batteries at a high current rate is still a major challenge. In this study, we discover a novel synergy among InX 3 (X = I and Br) bifunctional RMs, molybdenum disulfide (MoS 2 ) nanoflakes as the air electrode, dimethyl sulfoxide/ionic liquid hybrid electrolyte, and LiTFSI as a salt to achieve long cycle-life operations of Li–O 2 batteries in a dry air environment at high charge–discharge rates. Our results indicate that batteries with InI3 operate up to 450 cycles with a current density of 0.5 A g –1 and 217 cycles with a current density of 1 A g –1 at a fixed capacity of 1 A h g –1 . Batteries with InBr 3 operate up to 600 cycles with a current density of 1 A g –1 . These batteries can also operate at a higher charge rate of 2 A g –1 up to 200 cycles (for InBr 3 ) and 160 cycles (for InI 3 ). Our experimental and computational results reveal that while X 3 – is the source of the redox mediator, LiX at the MoS 2 cathode, In 3+ reacts on the lithium anode side to form a protective layer on the surface, thus acting as an effective bifunctional RM in a dry air environment. This evidence for a simultaneous improvement in the current rates and cycle life of a battery in a dry air atmosphere opens a new direction for research for advanced energy storage systems.

25 ENERGY STORAGE↗
DOE OSTI2020

Materials Data on Li2O by Materials Project

Li2O is Fluorite structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Li1+ is bonded to four equivalent O2- atoms to form a mixture of corner and edge-sharing LiO4 tetrahedra. All Li–O bond lengths are 2.02 Å. O2- is bonded in a body-centered cubic geometry to eight equivalent Li1+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Li2O2 by Materials Project

Li2O2 crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Li is bonded to four equivalent O atoms to form a mixture of distorted edge and corner-sharing LiO4 tetrahedra. There is three shorter (1.97 Å) and one longer (2.02 Å) Li–O bond length. O is bonded in a 5-coordinate geometry to four equivalent Li and one O atom. The O–O bond length is 1.52 Å.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Li2O2 by Materials Project

Li2O2 crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. there are two inequivalent Li sites. In the first Li site, Li is bonded to six equivalent O atoms to form edge-sharing LiO6 octahedra. All Li–O bond lengths are 2.17 Å. In the second Li site, Li is bonded in a 6-coordinate geometry to six equivalent O atoms. All Li–O bond lengths are 1.99 Å. O is bonded in a 7-coordinate geometry to six Li and one O atom. The O–O bond length is 1.55 Å.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on LiO3 by Materials Project

LiO3 crystallizes in the orthorhombic Imm2 space group. The structure is three-dimensional. Li is bonded in a 6-coordinate geometry to six equivalent O atoms. There are four shorter (2.23 Å) and two longer (2.25 Å) Li–O bond lengths. There are two inequivalent O sites. In the first O site, O is bonded in a distorted water-like geometry to two equivalent O atoms. Both O–O bond lengths are 1.36 Å. In the second O site, O is bonded to three equivalent Li and one O atom to form a mixture of distorted edge and corner-sharing OLi3O tetrahedra.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Li2O by Materials Project

Li2O is Cotunnite structured and crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. there are two inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded in a 3-coordinate geometry to five equivalent O2- atoms. There are a spread of Li–O bond distances ranging from 1.98–2.44 Å. In the second Li1+ site, Li1+ is bonded to four equivalent O2- atoms to form a mixture of edge and corner-sharing LiO4 tetrahedra. There is three shorter (1.98 Å) and one longer (2.00 Å) Li–O bond length. O2- is bonded in a 9-coordinate geometry to nine Li1+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on LiO2 by Materials Project

LiO2 is Marcasite structured and crystallizes in the orthorhombic Pnnm space group. The structure is three-dimensional. Li is bonded to six equivalent O atoms to form LiO6 octahedra that share corners with eight equivalent LiO6 octahedra, corners with six equivalent OLi3O tetrahedra, and edges with two equivalent LiO6 octahedra. The corner-sharing octahedral tilt angles are 69°. There are two shorter (2.10 Å) and four longer (2.13 Å) Li–O bond lengths. O is bonded to three equivalent Li and one O atom to form distorted OLi3O tetrahedra that share corners with three equivalent LiO6 octahedra, corners with thirteen equivalent OLi3O tetrahedra, and an edgeedge with one OLi3O tetrahedra. The corner-sharing octahedra tilt angles range from 65–66°. The O–O bond length is 1.34 Å.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Li2O2 by Materials Project

Li2O2 is Tetraauricupride structured and crystallizes in the tetragonal P4/nmm space group. The structure is three-dimensional. Li is bonded in a body-centered cubic geometry to eight equivalent O atoms. There are four shorter (2.19 Å) and four longer (2.21 Å) Li–O bond lengths. O is bonded in a body-centered cubic geometry to eight equivalent Li atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on LiO2 by Materials Project

LiO2 crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. Li is bonded in a 8-coordinate geometry to eight O atoms. There are a spread of Li–O bond distances ranging from 2.09–2.27 Å. There are two inequivalent O sites. In the first O site, O is bonded in a 6-coordinate geometry to four equivalent Li and two equivalent O atoms. Both O–O bond lengths are 1.75 Å. In the second O site, O is bonded in a 4-coordinate geometry to four equivalent Li and two equivalent O atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Li2O2 by Materials Project

Li2O2 is Tetraauricupride structured and crystallizes in the tetragonal P4mm space group. The structure is three-dimensional. Li is bonded in a distorted body-centered cubic geometry to eight O atoms. There are a spread of Li–O bond distances ranging from 2.16–2.18 Å. There are two inequivalent O sites. In the first O site, O is bonded in a body-centered cubic geometry to eight equivalent Li atoms. In the second O site, O is bonded in a body-centered cubic geometry to eight equivalent Li atoms.

36 MATERIALS SCIENCE↗