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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Resolving the Valence of Iron Oxides by Resonant Photoemission Spectroscopy

Precisely determining the oxidation states of metal cations within variable-valence transition metal oxides remains a significant challenge, yet it is crucial for understanding and predicting the properties of these technologically important materials. Iron oxides, in particular, exhibit a remarkable diversity of electronic structures due to the variable valence states of iron (Fe 2+ and Fe 3+ ). A quantitative analysis using conventional X-ray photoelectron spectroscopy (XPS) is challenging because of the strong overlap of the Fe 2p XPS peaks from different oxidation states. Here, in this study, we show how this problem can be resolved using Resonant Photoemission Spectroscopy (ResPES), which unambiguously distinguishes Fe oxidation states and spectroscopically estimates the composition ratio of Fe cation valence states in the complex Fe oxides. We demonstrate this in the model case of a FeO 2 monolayer film on Pt(111), showing that the FeO 2 film consists of an equal mixture of Fe 2+ and Fe 3+ cations, yielding an average valence of +2.5, contrary to the +3 valence proposed based on density functional theory (DFT).

Chen, Hao [Lawrence Berkeley National Laboratory (↗
DOE OSTI2021

Elucidating the Redox Behavior during Atomic Layer Deposition on Lithium-Ion Battery Cathode Materials

Atomic layer deposition (ALD) has emerged as a promising technology for applying ultrathin protective coatings on lithium-ion battery (LIB) cathode surfaces to improve their cycling stability. While there have been numerous reports evaluating the electrochemical performance of these surface-modified cathode materials, the chemical changes induced on the surface of the cathode materials upon ALD coating are not fully studied. This paper describes a systematic investigation to understand the interfacial changes of 12 different cathode materials upon coating with aluminum oxide (Al 2 O 3 ) using trimethyl aluminum (TMA) and H 2 O, and aluminum fluoride (AlF 3 ) using TMA and hydrogen fluoride pyridine (HFPy). Here, the surface composition of these cathode materials, which range from simple transition metal oxides (e.g. NiO and MnO) to complex multi-element cathode materials (e.g. LiNi x Mn 1-x-y Co y O 2 , NMC), was studied via X-ray photoelectron spectroscopy (XPS). The XPS measurements reveal that the transition metals in the cathode materials undergo selective oxidation/reduction depending upon the nature of the precursor, the coating, and the cathode material. The ability to chemically modify the surface of cathode materials via vapor-phase precursor adsorption will open new avenues to systematically control the interface of the cathode materials in LIBs that are not possible by conventional coating methods.

25 ENERGY STORAGE↗
DOE OSTI2020

Consequences of long-term water exposure for bulk crystal structure and surface composition/chemistry of nickel-rich layered oxide materials for Li-ion batteries

Water exposure of layered nickel-rich transition metal oxide electrodes, widely used in high-energy lithium-ion batteries, has detrimental effects on the electrochemical performance, which complicates electrode handling and prevents implementation of environmentally benign aqueous processing procedures. Elucidating the degradation mechanisms in play may help rationally mitigate/circumvent key challenges. Here, the bulk structural consequences of long-term (>2.5 years) deuterated water (D2O) exposure of intercalation materials with compositions Li x Ni 0.5 Co 0.2 Mn 0.3 O 2 (NCM523) and Li x Ni 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) are studied by neutron powder diffraction (NPD). Detailed inspection of the NPD data reveals gradual formation of a secondary crystalline phase in all exposed samples, not previously reported for this system. This unknown phase forms faster in liquid- compared to vapor-exposed compounds. Structural modelling of the NPD data shows a stable level of Li/Ni anti-site defects and does not indicate any significant changes in lattice parameters or hydrogen-lithium (D + /Li + ) exchange in the structure. Consequently, the secondary phase formation must take place via transformation rather than modification of the parent material. X-ray photoelectron spectroscopy data indicate formation of LiHCO 3 /Li 2 CO 3 at the surface and a Li-deficient oxide in the sub-surface region of the pristine compounds, and the presence of adsorbed water and transition metal hydroxides at the exposed sample surfaces.

25 ENERGY STORAGE↗
DOE OSTI2022

Electrochemical Proton Insertion Modulates the Hydrogen Evolution Reaction on Tungsten Oxides

Development of new electrocatalysts for the hydrogen evolution reaction (HER) could reduce dependence on Pt and other rare metals and enable large-scale production of hydrogen with near-zero carbon emissions. Mechanistic insight into the electrocatalytic activity of a material helps to accelerate the development of new electrocatalysts. Alternative electrocatalyst materials such as transition metal oxides and sulfides can undergo insertion reactions that change their properties. Recent reports indicate that the presence of inserted ions can influence electrocatalytic activity. In this work, we utilized a materials chemistry approach to understand the role of proton insertion on the HER activity of layered tungsten oxide hydrates (WO 3 ∙xH 2 O, x = 1, 2). We synthesized a series of tungsten oxide hydrates along with an octylamine-pillared tungsten oxide (OA-WO 3 ). We used cyclic voltammetry to study the electrochemical reactivity of each material and performed ex situ X-ray diffraction and Raman spectroscopy to understand bulk and surface structural changes during electrochemical cycling. We show an inverse relationship between the degree of proton insertion and HER overpotential in tungsten oxides: the lack of proton insertion leads to a high overpotential for the HER. We discuss three hypotheses for how proton insertion leads to HER activity in WO 3 ∙xH 2 O: 1) proton insertion changes the electronic band structure of WO 3 ∙xH 2 O, 2) the presence of bulk protons can influence ΔG H,ads at the surface sites, and 3) inserted protons may participate in the HER mechanism on WO 3 ∙xH 2 O. Overall, this work shows the critical role of proton insertion in enabling high HER activity in tungsten oxides.

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

Time-Resolved X-ray Operando Observations of Lithiation Gradients across the Cathode Matrix and Individual Oxide Particles during Fast Cycling of a Li-Ion Cell

Lithiated transition metal oxides serve as active materials in the positive electrode (cathode) of lithium-ion cells. During electrochemical cycling, lithium ions intercalate and deintercalate into these oxide particles. This behavior causes two types of lithiation gradients to emerge: (i) a bulk gradient across the depth of the cathode matrix (averaged over individual oxide particles) and (ii) a microscopic gradient across the particles themselves, which also depends on their location in the electrode. Here we show how both gradients can be studied using operando X-ray diffraction during 4C charge and 4C discharge. The oxide (de)lithiation is estimated from the unit cell parameters by indexing the X-ray diffraction spectra. By fitting the lithiation profiles with orthogonal polynomials, the bulk gradients across the electrode thickness are quantified. These gradients develop as the current flows through the cell and dissipate during open-circuit and potentiostatic-hold periods. Further details of lithiation dynamics can be obtained through shape analysis of the Bragg peaks. In particular, from electrochemical model simulations, we show that the width and skewness of the (003) peak track (de)lithiation fronts moving across the individual oxide particles.

(003) peak↗
DOE OSTI2025

Compact in situ probe for magnetotransport measurements of 2D materials under variable tensile strain

The recent development of freestanding oxide membranes has opened new opportunities for strain engineering of transition metal oxides beyond values accessible in bulk samples. While a number of studies have been performed with fixed strain, the ability to dynamically control the strain state during measurement would be greatly enabling. To this end, we present an in situ uniaxial strain probe optimized for transport measurements of tensile-strained 2D or quasi-2D materials down to 2 K. Utilizing a flexible polyimide substrate as the stress transfer medium, our platform simplifies the sample preparation process and allows precise alignment of strain fields relative to the crystalline axes. An in situ optical microscope monitors the macroscopic strain state operando and makes it possible to complete an entire magnetotransport study at cryogenic temperatures under continuous strain variations. We demonstrate the capabilities of the probe on a freestanding LaNiO 3 membrane, where we induce tensile strain up to 8% and observe a corresponding strong transport anisotropy. In view of the rapid developments in low-dimensional materials synthesis and the plethora of novel quantum phenomena they exhibit, this strain probe provides general instrumentation for examining and controlling these properties via strain.

2D materials↗
DOE OSTI2022

Exploring the Origin of Anionic Redox Activity in Super Li-Rich Iron Oxide-Based High-Energy-Density Cathode Materials

Super alkali-rich materials (alkali:transition metal ratio of ≥2:1), such as Li 5 FeO 4 , exhibit the potential to realize anionic redox upon deep delithiation. Li 5 FeO 4 was shown to undergo reversible cycling between Li 4 FeO 3.5 and Li 3 FeO 3.5 with combined cation/anion redox, a remarkable capacity of 189 mAh/g, and no O 2 release. However, the impact of phase transformations on the reaction thermodynamics and the correlation between the structural changes and reaction reversibility remain unclear. In this study, we use first-principles calculations to examine the delithiation and (re)lithiation reactions of Li 5 FeO 4 . We show that the experimentally observed charge and discharge processes go through non-equilibrium pathways. Upon delithiation, the compound undergoes a phase transformation from Li 5 FeO 4 , with tetrahedrally coordinated (T d ) Fe ions, to a delithiated disordered rocksalt structure, with octahedral (O h ) Fe ions. Fe-ion migration has an asymmetric kinetic barrier that makes T d → O h migration facile, whereas the reverse process has a much larger barrier, explaining the difficulties in reaction reversibility. We further elucidate the transition metal and O redox sequences during the charge cycle and identify the complex electrochemistry associated with the dual participation of cationic redox (Fe 3+ /Fe 4+ ) and anionic redox (O 2– /O – /O o ). Armed with this knowledge, we conduct high-throughput screening of known alkali-rich transition metal oxides by evaluating their potential to enable reversible anionic redox, with multiple candidates proposed for further experimental trials. Furthermore, our work provides a useful guide for the further development of super alkali-rich anionic-redox-active electrodes for high-energy-density batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

Oxygen Loss in Layered Oxide Cathodes for Li-Ion Batteries: Mechanisms, Effects, and Mitigation

Layered lithium transition metal oxides derived from LiMO 2 (M = Co, Ni, Mn, etc.) have been widely adopted as the cathodes of Li-ion batteries for portable electronics, electric vehicles, and energy storage. Oxygen loss in the layered oxides is one of the major factors leading to cycling-induced structural degradation and its associated fade in electrochemical performance. Herein, we review recent progress in understanding the phenomena of oxygen loss and the resulting structural degradation in layered oxide cathodes. We first present the major driving forces leading to the oxygen loss and then describe the associated structural degradation resulting from the oxygen loss. Here, we follow this analysis with a discussion of the kinetic pathways that enable oxygen loss, and then we address the resulting electrochemical fade. Finally, we review the possible approaches toward mitigating oxygen loss and the associated electrochemical fade as well as detail novel analytical methods for probing the oxygen loss.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Fast oxygen redox enabled by flexible Al–O bonds in P2-type layered oxides for sodium batteries

Sodium-ion batteries (SIBs) exhibit significant potential for large-scale energy storage systems due to the abundance and low cost of sodium resources. Triggering lattice oxygen redox (LOR) in P2-type transition metal oxides is considered a promising approach to enhance energy density in SIB cathodes, providing high operating potential and substantial capacity. However, irreversible phase transitions associated with LOR, particularly from prisms (P-type stacking) to octahedrons (O-type stacking), lead to severe structural distortions and sluggish Na + diffusion kinetics. In this work, an Al-substitution strategy is proposed to suppress the formation of O-type stacking and instead promote the formation of a beneficial Z phase. Furthermore, the flexible Al-O bonds accommodate asymmetric variations in their occupied states during the sodiation process, mitigating local structural distortions through Al-O bond contraction. Stabilization of the local structure ensures the maintenance of a robust Na + diffusion pathway. As a result, the Al-substituted cathode achieves a low Na + diffusion barrier of 0.47 eV and delivers a capacity of 86 mAh/g even at a high current density of 1 A/g within 1.5–4.5 V, maintaining 62.5% capacity retention over 100 cycles.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A Library of Atomically Thin 2D Materials Featuring the Conductive-Point Resistive Switching Phenomenon

Non-volatile resistive switching (NVRS) is a widely available effect in transitional metal oxides, colloquially known as memristors, and of broad interest for memory technology and neuromorphic computing. Until recently, NVRS was not known in other transitional metal dichalcogenides (TMDs), an important material class owing to their atomic thinness enabling the ultimate dimensional scaling. Here, various monolayer or few-layer 2D materials are presented in the conventional vertical structure that exhibit NVRS, including TMDs (MX 2 , M = transitional metal, e.g., Mo, W, Re, Sn, or Pt; X = chalcogen, e.g., S, Se, or Te), TMD heterostructure (WS2/MoS2), and an atomically thin insulator (h-BN). These results indicate the universality of the phenomenon in 2D non-conductive materials, and feature low switching voltage, large ON/OFF ratio, and forming-free characteristic. A dissociation–diffusion–adsorption model is proposed, attributing the enhanced conductance to metal atoms/ions adsorption into intrinsic vacancies, a conductive-point mechanism supported by first-principle calculations and scanning tunneling microscopy characterizations. Our results motivate further research in the understanding and applications of defects in 2D materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Covalency in Fe 2 O 3 and FeO: Consequences for XPS satellite intensity

The covalent character of the interaction between the metal cation and the oxygen ligands has been examined for two Fe oxides with different nominal oxidation states, Fe(II)O, and Fe(III) 2 O 3 . The covalent character is examined for the initial, ground state configuration and for the ionic states involving the removal of a shallow core, Fe 3p, and a deep core, Fe 2p, electron. The covalency is assessed based on novel theoretical analyses of wave functions for the various cases. It is found that the covalency is considerably different for different oxidation states and for different ionized and non-ionized configurations. The changes in covalency for the ions are shown to be responsible for important changes in relaxation energies for X-Ray Photoelectron Spectroscopy (XPS) spectra and in the intensity lost from main XPS peaks to shake satellites. While these consequences are not observables themselves, they are important for the interpretation of the XPS spectra, in particular, for efforts to extract stoichiometries of these iron oxides from XPS data. This is a finding likely applicable across various 3d transition metal oxide materials.

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

Real Space Imaging of Spin Stripe Domain Fluctuations in a Complex Oxide

Understanding the formation and dynamics of charge and spin-ordered states in low-dimensional transition metal oxide materials is crucial to understanding unconventional high-temperature superconductivity. La 2-x Sr x NiO 4+δ (LSNO) has attracted much attention due to its interesting spin dynamics. Recent x-ray photon correlation spectroscopy studies have revealed slow dynamics of the spin order (SO) stripes in LSNO. Here, we applied resonant soft x-ray ptychography to map the spatial distribution of the SO stripe domain inhomogeneity in real space. The reconstructed images show the SO domains are spatially anisotropic, in agreement with previous diffraction studies. For the SO stripe domains, it is found that the correlation lengths along different directions are strongly coupled in space. Surprisingly, fluctuations were observed in the real space amplitude signal, rather than the phase or position. Overall, we attribute the observed slow dynamics of the stripe domains in LSNO to thermal fluctuations of the SO domain boundaries.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Antiferromagnetic Inverse Spinel Oxide LiCoVO 4 with Spin-Polarized Channels for Water Oxidation

Exploring highly efficient catalysts for the oxygen evolution reaction (OER) is essential for water electrolysis. Cost-effective transition-metal oxides with reasonable activity are raising attention. Recently, OER reactants' and products' differing spin configurations have been thought to cause slow reaction kinetics. Catalysts with magnetically polarized channels could selectively remove electrons with opposite magnetic moment and conserve overall spin during OER, enhancing triplet state oxygen molecule evolution. Herein, antiferromagnetic inverse spinel oxide LiCoVO 4 is found to contain d 7 Co 2+ ions that can be stabilized under active octahedral sites, possessing high spin states S = 3/2 (t 2g 5 e g 2 ). With high spin configuration, each Co 2+ ion has an ideal magnetic moment of 3 µ B , allowing the edge-shared Co 2+ octahedra in spinel to be magnetically polarized. Density functional theory simulation results show that the layered antiferromagnetic LiCoVO 4 studied contains magnetically polarized channels. The average magnetic moment (µ ave ) per transition-metal atom in the spin conduction channel is around 2.66 µ B . Such channels are able to enhance the selective removal of spin-oriented electrons from the reactants during the OER, which facilitates the accumulation of appropriate magnetic moments for triplet oxygen molecule evolution. Finally, the LiCoVO 4 reported has been identified as an oxide catalyst with excellent OER activity.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Deciphering phase evolution in complex metal oxide thin films via high-throughput materials synthesis and characterization

Discovery of structure-property relationships in thin film alloys of complex metal oxides enabled by high-throughput materials synthesis and characterization facilities is demonstrated here with a case-study. In this study, thin films of binary transition metal oxides (Ti–Zn) are prepared by pulsed laser deposition with continuously varying Ti:Zn ratio, creating combinatorial samples for exploration of the properties of this material family. The atomic structure and electronic properties are probed by spatially resolved techniques including x-ray absorption near edge structures (XANES) and x-ray fluorescence (XRF) at the Ti and Zn K-edge, x-ray diffraction, and spectroscopic ellipsometry. The observed properties as a function of Ti:Zn ratio are resolved into mixtures of five distinguishable phases by deploying multivariate curve resolution analysis on the XANES spectral series, under constraints set by results from the other characterization techniques. First-principles computations based on density function theory connect the observed properties of each distinct phase with structural and spectral characteristics of crystalline polymorphs of Ti–Zn oxide. Continuous tuning of the optical absorption edge as a function of Ti:Zn ratio, including the unusual observation of negative optical bowing, exemplifies a functional property of the film correlated to the phase evolution.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Metal Oxide Particles as Atmospheric Nuclei: Exploring the Role of Metal Speciation in Heterogeneous Efflorescence and Ice Nucleation

Mineral dust can indirectly impact climate by nucleation of atmospheric solids, for example, by heterogeneously nucleating ice in mixed-phase clouds or by impacting the phase of aerosols and clouds through contact nucleation. The effectiveness toward nucleation of individual components of mineral dust requires further study. Here, the nucleation behavior of metal oxide nanoparticle components of atmospheric mineral dust is investigated. A long-working-distance optical trap is used to study contact and immersion nucleation of ammonium sulfate by transition-metal oxides, and an environmental chamber is used to probe depositional ice nucleation on metal oxide particles. Previous theory dictates that ice nucleation and heterogeneous nucleation of atmospheric salts can be impacted by several factors including morphology, lattice match, and surface area. Here, we observe a correlation between the cationic oxidation states of the metal oxide heterogeneous nuclei and their effectiveness in causing nucleation in both contact efflorescence mode and depositional freezing mode. In contrast to the activity of contact efflorescence, the same metal oxide particles did not cause a significant increase in efflorescence relative humidity when immersed in the droplet. In conclusion, these experiments suggest that metal speciation, possibly as a result of cationic charge sites, may play a role in the effectiveness of nucleation that is initiated at particle surfaces.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Ultrashort XUV pulse absorption spectroscopy of partially oxidized cobalt nanoparticles

High-order harmonic generation (HHG) based transient extreme ultraviolet (XUV) absorption spectroscopy is an emerging technique to trace photoinduced charge carrier dynamics in condensed phase materials with femtosecond and even attosecond temporal resolution and elemental specificity. However, its application to nanoparticulate samples that are relevant, for example, for novel photocatalytic light harvesting concepts, has been limited. This is in part due to the challenge to produce residual-free samples on ultrathin, XUV-transparent substrates as well as a widespread understanding that sparsely distributed nanoparticles do not provide sufficient contrast for XUV absorption measurements. Here, we present static XUV absorption spectra of partially oxidized Co nanowire-structures with diameters of approximately 4.5 nm and lengths between 10 and 40 nm, recorded with an ultrashort pulse HHG light source. Nanoparticles are synthesized by the agglomeration of Co atoms inside superfluid helium droplets, followed by surface deposition and oxidation in ambient air. The method is uniquely suited for residual-free synthesis of transition metal nanowires and their deposition on ultrathin substrates. Analysis by high-resolution transmission electron microscopy reveals the formation of CoO nanowires with regions of unoxidized Co in their interior. The nanoparticle samples are investigated in an HHG-driven ultrafast XUV absorption setup. Despite the low surface coverage of only 23%, the recorded spectrum exhibits a distinct absorption feature at the Co M 2,3 (2p) edge near 60 eV with a peak height of about 40 mOD. Finally, the results support the feasibility of table-top ultrafast transient XUV absorption studies of photoinduced dynamics in transition metal oxide nanoparticles with sub-monolayer surface coverage.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Temporal Ni K-Edge X-ray Absorption Spectroscopy Study Reveals the Kinetics of the Ni Redox Behavior of the Iron-Nickel Oxide Bimetallic OER Catalyst

Operando X-ray absorption spectroscopy (XAS) can be utilized to probe the phase and structural changes of FeNiOx and similar transition metal oxide electrocatalysts during electrocatalytic reactions. However, capturing the temporal changes occurring in the operando chemistry of electrocatalysts has been little studied. Here, in this work, we successfully capture the time-resolved changes at the Ni K-edge for both the X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) regions of an aqueous phase synthesized FeNiO x bimetallic nanoparticle electrocatalyst. During a stepped voltage experiment, the temporal change in the Ni K-edge was observed as the applied voltage was stepped from 0.7 to 0.8 V versus the silver/silver chloride reference electrode, and the change observed is associated with the Ni redox transition from the 2+ to 3+/4+ oxidation state. Individual XAS spectra were obtained in 90 s, and a total of 9 scans post voltage step showed a unique transition from a hydroxide to an oxyhydroxide phase. The shift in absorption edge energy position and the changes in spectral shape for individual scans explain the typically observed broadening of the Ni K-edge XANES spectrum during time-averaged operando XAS, and a kinetic analysis revealed a first-order observed rate constant, |k obs |, of 0.00426 s –1 and a half-life (t 1/2 ) of 163 s. Multivariate curve resolution-alternating least squares analysis followed by linear combination fitting analysis for time-averaged versus time-resolved Ni K-edge changes upon voltage step show distinct differences in estimated contributions from Ni 2+ oxide/hydroxide phases. Detailed EXAFS modeling shows the phase transition from hydroxide to oxyhydroxide on top of the unchanged metallic core.

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

Band-mixing effects in one-dimensional charge transfer insulators

The low-energy properties of transition metal oxides (TMOs) are governed by the electrons occupying strongly correlated $d$-orbitals that are hybridized with surrounding ligand oxygen $p$ orbitals to varying degrees. Their physics is thus established by a complex interplay between the transition-metal (TM)-ligand hopping $t$, charge transfer energy $\Delta_\mathrm{CT}$, and on-site TM Hubbard repulsion $U$. Here, we study the spectral properties of a one-dimensional (1D) analog of such a $pd$ system, with alternating TM $d$ and ligand anion $p$ orbitals situated along a chain. Using the density matrix renormalization group method, we study the model's single-particle spectral function, x-ray absorption spectrum, and dynamical spin structure factor as a function of $\Delta_\mathrm{CT}$ and $U$. In particular, we present results spanning from the Mott insulating ($\Delta_\mathrm{CT} > U$) to negative charge transfer regime $\Delta_\mathrm{CT} < 0$ to gain a better understanding of the ground and momentum-resolved excited state properties of these different regimes. Our results can guide new studies on TMOs that seek to situate them within the Mott-Hubbard/charge transfer insulator classification scheme.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗