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At least 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Electronic structure and magnetism of pristine, defected, and strained $\mathrm{Ti_2N}$ $\mathrm{MX}$ene

Here, from first principles electronic structure calculations, we unravel the evolution of structural, electronic, and magnetic properties of pristine, defected, and strained titanium nitride MXene with different functional groups (-F, -O, -H, and -OH). The formation and cohesive energies reveal their chemical stability. The dynamical stability of Ti 2 N mono-layer is also confirmed by phonon calculations. The MAX phase and defect free functionalized MXenes are metallic except for oxygen terminated (Ti 2 NO 2 ) one which is 100% spin polarized half-metallic ferromagnet. The spin–orbit coupling significantly influences the bare MXene (Ti 2 N) to exhibit Dirac topology and band inversion near the high symmetry directions. The strain effect sways the Fermi level thereby shifting it towards lower energy state under compression and towards higher energy state under tensile strain in Ti 2 NH 2 . The Ti 2 NO 2 exhibits exotic electronic structure not only in pristine but also in strained and defected structures. Its half-metallic nature changes to semi-metallic under 1% compression and it is completely destroyed under 2% compression. In single vacancy defect, its band structure remarkably transforms from half-metallic to semi-conducting with large band gap in 12.5% Ti, weakly semi-conducting in 5.5% Ti, and semi-metallic in 12.5% O. The 25% N defect changes its half-metallic characteristic to metallic. Further, the 12.5% Co substitution preserves its half-metallic character, whereas Mn substitution allows it to convert half-metallic characteristic into weak semi-metallic characteristic preserving ferromagnetism. However, Cr substitution converts half-metallic ferromagnetic state to half-metallic anti-ferromagnetic state. The understanding made here on collective structural stability, and electronic band structure, and magnetic phenomena in novel 2D Ti 2 N derived MXenes open up their possibility in designing them for synthesis.

36 MATERIALS SCIENCE↗
NASA NTRS1981

Annealing and anomalous high-energy electron irradiation effects in low-cost silicon N+P solar cells

Silicon solar cells of N(+)P type were subjected to 1 MeV electron irradiation (up to 10 to the 16th electrons/sq cm) and then annealed at 450 C for 20 min or annealed with no electron irradiation. Electron irradiation resulted in a degradation of longer wavelength cell response, but produced a marked enhancement of response at shorter wavelengths with a peak change of 40% at 0.44 microns. Subsequent thermal anneal at 450 C reduced the long-wavelength degradation, but enhancement at shorter wavelengths persisted. Excitation at the shorter wavelengths was in the N(+)-diffused layer and in the junction region of the cell. Anneal of unirradiated cells produced shorter-wavelength enhancement with a similar peaking at 0.44 microns, but with a relative change of only 20%. More enhancement was produced in the longer wavelength region (up to 0.8 microns). These effects in the different cell regions are explained by a decrease in the interstitial oxygen-impurity complexes (deep recombination levels) and the formation of substantial oxygen-silicon vacancy centers (donors).

Garlick, G. F. J.↗
DOE OSTI2026

Task Sharing of Proton Incorporation in Vertically Aligned Nanocomposite Triple Conductors: Growth, Structure, and Surface Exchange Kinetics

As protonic ceramic electrolysis cells emerge for efficient H 2 production, there is a need to develop air electrode materials enabling fast, durable steam splitting and proton incorporation. Single-phase triple conductors may fail to satisfy the myriad performance/stability requirements, and their critical charge-carriers (holes, oxygen vacancies, and protons) are in competition, limiting their concentrations. Instead, we propose task-sharing, vertically aligned nanocomposites (VANs), comprising a proton conductor (BaZr 0.9 Y 0.1 O 3-δ ) and a redox-active mixed ionic electronic conductor (Ce 0.9 Pr 0.1 O 2-δ ), that may enable rapid proton surface exchange at the solid–gas interface and transport along the solid–solid heterointerfaces. We grew VANs by pulsed laser deposition and investigated the interplay between their processing conditions, structure, and proton and oxygen surface exchange kinetics. We varied the substrate temperature, laser repetition rate, laser fluence, and processing oxygen pressure. The crystallinity and phases were characterized by grazing-incidence X-ray diffraction, and the strain and structural order as a function of depth were evaluated by angle-dependent synchrotron X-ray pair distribution function analysis. To evaluate the potential for interdiffusion, the formation energies of substitutional defects were simulated with density functional theory. Corresponding structural analysis and elemental mapping were performed by scanning/transmission electron microscopy, energy-dispersive X-ray spectroscopy, and electron energy-loss spectroscopy, indicating distinct nanoscale compositional regions with a hierarchical structure embedded in individual VANs columns and minimal interdiffusion across a bilayer film. Proton and oxygen surface exchange coefficients (k H , k O ) and polarization resistances were evaluated by electrical and optical relaxations and impedance spectroscopy of VAN-incorporated protonic ceramic electrochemical cells, respectively, at 400–500 °C, demonstrating values comparable to some of the best-known triple and mixed conductors.

36 MATERIALS SCIENCE↗
DOE OSTI2022

The mechanism behind the high radiation tolerance of Fe-Cr alloys

With the great demand for high radiation tolerant materials for advanced nuclear energy technologies, Fe-Cr alloys are at the forefront with long standing validated performance. Yet, the real mechanism behind their high radiation resistance is in question and understanding the effect of varying Cr percentage is a grand challenge limiting further improvements. Here we applied depth resolved atomic scale probe of defects to uncover the real mechanism on how Cr improves radiation resistance and explain the controversial impact of increasing Cr percentage. By combining depth-resolved positron annihilation lifetime spectroscopy and Doppler broadening spectroscopy we investigated the effect of Cr alloying on the formation and evolution of atomic size clusters induced by ion irradiation in Fe. We also used atom probe tomography to investigate the possible presence of Cr clusters or a’ phase with high Cr composition. The study reveals that the well-known resistance to radiation in Fe-Cr alloys arises from the stabilization of vacancy clusters around Cr atoms which act as sinks for radiation-induced defects. Thus, Cr atoms do not provide a direct sink for interstitials; rather defect complexes for that consist of Cr atoms and vacancies in turn act as sinks for irradiation-induced vacancies and interstitials. Most importantly, we find that lower amounts of Cr create smaller, uniformly distributed defect clusters that act as efficient sinks for radiation damage, but larger quantities of Cr form a defect structure that is less homogenous in size and spatial distribution, resulting in less efficient damage recombination. No evidence of phase a’ was found before or after irradiation, which indicates that it does not contribute to the observed radiation tolerance.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Evaluation of δ-Phase ZrH1.4 to ZrH1.7 Thermal Neutron Scattering Laws Using Ab Initio Molecular Dynamics Simulations

Zirconium hydride is commonly used for next-generation reactor designs due to its excellent hydrogen retention capacity at temperatures below 1000 K. These types of reactors operate at thermal neutron energies and require accurate representation of thermal scattering laws (TSLs) to optimize moderator performance and evaluate the safety indicators for reactor design. In this work, we present an atomic-scale representation of sub-stoichiometric ZrH2−x(0.3≤x≤0.6), which relies on ab initio molecular dynamics (AIMD) in tandem with velocity auto-correlation (VAC) analysis to generate phonon density of states (DOS) for TSL development. The novel NJOY+NCrystal tool, developed by the European Spallation Source community, was utilized to generate the TSL formulations in the A Compact ENDF (ACE) format for its utility in neutron transport software. First, stoichiometric zirconium hydride cross sections were benchmarked with experiments. Then sub-stoichiometric zirconium hydride TSLs were developed. Significant deviations were observed between the new δ-phase ZrH2−x TSLs and the TSLs in the current ENDF release. It was also observed that varying the hydrogen vacancy defect concentration and sites did not cause as significant a change in the TSLs (e.g., ZrH1.4 vs. ZrH1.7) as was caused by the lattice transformation from ϵ- to δ-phase.

42 ENGINEERING↗
DOE OSTI2021

Progressive growth of the solid–electrolyte interphase towards the Si anode interior causes capacity fading

The solid–electrolyte interphase (SEI), a layer formed on the electrode surface, is essential for electrochemical reactions in batteries and critically governs the battery stability. Active materials, especially those with extremely high energy density, such as silicon (Si), often inevitably undergo a large volume swing upon ion insertion and extraction, raising a critical question as to how the SEI interactively responds to and evolves with the material and consequently controls the cycling stability of the battery. Here, by integrating sensitive elemental tomography, an advanced algorithm and cryogenic scanning transmission electron microscopy, we unveil, in three dimensions, a correlated structural and chemical evolution of Si and SEI. Furthermore, corroborated with a chemomechanical model, we demonstrate progressive electrolyte permeation and SEI growth along the percolation channel of the nanovoids due to vacancy injection and condensation during the delithiation process. Consequently, the Si–SEI spatial configuration evolves from the classic ‘core–shell’ structure in the first few cycles to a ‘plum-pudding’ structure following extended cycling, featuring the engulfing of Si domains by the SEI, which leads to the disruption of electron conduction pathways and formation of dead Si, contributing to capacity loss. The spatially coupled interactive evolution model of SEI and active materials, in principle, applies to a broad class of high-capacity electrode materials, leading to a critical insight for remedying the fading of high-capacity electrodes.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Laser-Assisted Synthesis of Monolayer 2D MoSe 2 Crystals with Tunable Vacancy Concentrations: Implications for Gas and Biosensing

We report tuning the structural and electronic properties of atomically thin two-dimensional (2D) materials via defect and vacancy engineering is the key to enabling their potential use in various applications, including electronics, energy, and sensing devices. Vacancies are, for instance, becoming highly promising for the enhanced interaction of gases and biomolecules with 2D materials in energy and sensing applications. However, the deterministic generation of desirable vacancies with tunable concentrations remains a challenge in 2D materials due to the limitations in the current growth methods, such as the complex reaction chemistries and gas flow dynamics. Therefore, engineering defects and vacancies in 2D materials have been mainly limited to destructive top-down processes such as heating, ion bombardments, and laser postprocessing. Here, we introduce a single-step bottom-up synthesis approach for the growth of monolayer MoSe 2 crystals with tunable vacancy concentrations. This method utilizes the spatiotemporal properties and adjustable power densities of the lasers to control the vaporization dynamics of the stoichiometric MoSe 2 powders. Such a mechanism in the vaporization allows us to grow tunable stoichiometry monolayer MoSe 2–x crystals on the substrates. The localized and time-controlled (250 ms to 2 s) vaporization of the MoSe 2 powder by a CO 2 laser enables the formation of monolayer crystals with controlled vacancy concentrations ranging from ~1 to 20%. The effects of laser power, laser irradiation time, and background pressure on the tuning range and subsequent properties of the crystals are investigated and quantified using Raman and photoluminescence spectroscopy, scanning transmission electron microscopy (STEM), and time-correlated single-photon counting (TCSPC). This bottom-up synthesis is a promising approach that allows the deterministic vacancy tuning for future electronics and, in particular, gas and biosensing applications without the need for further postprocessing and potential structural disruption of the crystals.

2D materials↗
NASA NTRS1990

Energetics and crystal chemistry of Ruddlesden-Popper type structures in high T(sub c) ceramic superconductors

The formation of Ruddlesden-Popper type layers (alternating slabs of rocksalt and perovskite structures) is seen in these oxides which is similar in many respects to what is seen in the system Sr-Ti-O. However, it was observed that there are some significant differences, for example the rocksalt and perovskite blocks in new superconducting compounds are not necessarily electrically, unlike in Sr-Ti-O systems. This will certainly render an additional coulombic bonding energy between two different types of blocks and may well lead to significant differences in their structural chemistry. In the higher order members of the various homologous series, additional Cu-O planes are inserted in the perovskite blocks. In order for the unit cell to electrically neutral the net positive charge on rocksalt block (which remains constant throughout the homologous series) should be balanced by an equal negative charge on perovskite block. It, thus becomes necessary to create oxygen vacancies in the basic perovskite structure, when width of the perovskite slab changes on addition of extra Cu-O planes. Results of atomistic simulations suggest that these missing oxygen ions allow the Cu-O planes to buckle in these compounds. This is also supported by the absence of buckling in the first member of Bi-containing compounds in which there are no missing oxygen ions and the Sr-Ti-O series of compounds. Additional results are presented on the phase stability of polytypoid structures in these crystal chemically complex systems. The studies will focus on the determination of the location of Cu(3+) in the structures of higher order members of the La-Cu-O system and whether Cu(3+) ions or oxygen vacancies are energetically more favorable charge compensating mechanism.

Dwivedi, Anurag↗
DOE OSTI2026

Facile Synthesis of Oxyhydrides by Reaction with NaBH 4 in an Open System

Oxyhydrides are an intriguing class of materials in which there is partial replacement of the oxide ion with hydride ions and oxygen vacancies. Conventional synthesis relies on vacuum sealed ampules, using long reaction times at high temperatures, limiting accessibility. Here, we demonstrate a rapid, ambient-pressure route to oxyhydride formation using NaBH 4 under flowing argon in just 1 h. This approach significantly lowers experimental barriers, enabling broader exploration of these materials. The maximum hydride incorporation, obtained using a reaction temperature of 400 °C, is given by the formula SrTiO 2.945 H 0.049 , where the hydride, oxygen vacancy, and unpaired electron concentrations are determined through thermogravimetric analysis, quantitative solid-state nuclear magnetic resonance (NMR) spectroscopy, and electron paramagnetic resonance (EPR) spectroscopy. Density functional theory simulations of the 1 H NMR shifts for candidate point defects support the assignment of the observed hydride peak, validating the efficacy of the synthetic approach. A combination of in situ and ex situ studies of the reaction pathway reveal that hydride incorporation into the perovskite occurs via direct solid-solid reaction, with higher reaction temperatures favoring NaBH 4 decomposition and H 2 (g) release over oxyhydride formation. The electronic defect structure established from the EPR and NMR studies indicate that, at ambient temperature, anion vacant sites are occupied by single electrons, whereas hydride sites do not trap electrons. As a result, this work establishes a scalable synthesis strategy and provides a computational-experimental framework for understanding defect chemistry in oxyhydrides, opening pathways for their integration into energy and electronic applications.

Anions↗
DOE OSTI2023

Effects of the surface termination and the oxygen vacancy position on LaNiO 3 ultra-thin films: First-principles study

In this study, while ultra-thin layers of the LaNiO 3 film exhibit a remarkable metal-insulator transition as the film thickness becomes smaller than a few unit cell (u.c.), the formation of possible oxygen vacancies and their effects on the correlated electronic structure have been rarely studied using first principles. Here, we investigate the effects of the surface termination and the oxygen vacancy position on the electronic properties and vacancy energetics of LaNiO 3 ultra-thin films under the compressive strain using density functional theory plus U (DFT + U). We find that oxygen vacancies can be easily formed in the Ni layers with the NiO 2 terminated surface (0.5 u.c. and 1.5 u.c. thickness) compared to the structures with the LaO terminated surface and the in-plane vacancy is energetically favored than the out-of-plane vacancy. When two vacancy sites are allowed, the Ni square plane geometry is energetically more stable in most cases as two oxygen vacancies tend to stay near a Ni ion. Strong anisotropy between the in-plane and out-of-plane vacancy formation as well as the layer and orbital dependent electronic structure occur due to strain, surface termination, charge reconstruction, and quantum confinement effects. The in-plane vacancy of the NiO 2 terminated structure is favored since the released charge due to the oxygen vacancy can be easily accommodated in the d x 2 -y 2 orbital, which is less occupied than the d z 2 orbital. Remarkably, the oxygen vacancy structure containing the Ni square-plane geometry becomes an insulating state in DFT + U with a sizable band gap of 1.2 eV because the large crystal field splitting between d z 2 and d x 2 -y 2 orbitals in the square-plane favors an insulating state and the Mott insulating state is induced in other Ni sites due to strong electronic correlations. In the thin-film structure without oxygen vacancies, the strong correlation effect in DFT + U drives a pseudogap ground state at the Fermi energy, similarly as the experimental photo-emission spectra; however, the variation of the DFT + U electronic structure depending on the surface termination becomes weaker compared to those obtained in DFT.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Defect-induced formation and frustration-driven multiple magnetic transitions in Gd 2 Co 0.90 Si 2.90

A new ternary compound, Gd 2 Co 0.90 Si 2.90 , has been synthesized in a chemically single phase by deliberately introducing lattice vacancies in the Co and Si sites. The system is characterized by DC magnetization, heat capacity, resistivity and density functional theory (DFT) calculations. Here, a detailed experimental study reveals that the system exhibits an antiferromagnetic transition below T N = 11.3 K followed by spin freezing behaviour below T B ~ 4.8 K. An additional high-temperature magnetic transition could also be detected at T H ~ 150 K, which is short range in character and is associated with defect-induced polarization of the conduction electrons. The spin-glass-like state formation in the system is additionally bolstered by the observation of magnetic relaxation and associated aging phenomena as well as the magnetic memory effect. On the basis of non-equilibrium dynamical behaviour, we argue that the glassy state in this compound favours the hierarchical model over the droplet model. DFT calculations and experimental outcomes establish that the ground state is magnetically frustrated due to the small energy difference between distinct spin configurations having closely spaced ground-state energies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Scaling microstructural processes in the sintering of ionic ceramics

A multi-scale framework, combining a multiphase field formulation and large deformation mechanics, was developed as a stepping stone to perform the data analytics of the microstructural level kinetics of a sintering solid. Relevant microstructural information from this framework, such as grain, stress, and porosity statistics, was scaled up to describe the macroscopic level sintering kinetics. Here, the developed formulation was applied to describe the electric field assisted sintering of Y 2 O 3 . Microstructural inhomogeneities in a multi-granular solid result in the formation of a field of compressive stress networks, which interleave with low compression and weakly tensile regions, defining a scaffolding for sintering concentration regions to develop. A Poisson effect-induced lateral stress network is also naturally self-induced as a result of the mechanical constraints imposed by the sintering apparatus. For long sintering times, localized shear stresses enhancing mass flow along grain boundaries and internal surfaces develop. Three-sided pores are removed by either vacancy transport to the surrounding pores, or move towards the external surfaces through grain boundary diffusion. Four- and higher order-sided pores stabilize because an equal amount of vacancies are gained and lost through the connecting grain boundaries. Grain dewetting contributes to pore coalescence, suggesting that pore kinetics and grain growth are coupled and should be analyzed in concert. The combined sintering and grain growth kinetics define six regimes of sintering behavior: (1) T, the transient regime; (2) E$_Υ$, the surface energy dominated, early sintering regime, where the grain growth exponent, p = 1, and the stress concentration factor, $f$ ~ $1/\hat{ρ}^{4.6}$; (3) E S , the stress dominated, early sintering regime, where p = 1 and $f$ ~ $1/\hat{ρ}^{4}$; (4) I$_Υ$, the surface energy dominated, intermediate sintering regime, where p = 2 and $f$ ~ $1/\hat{ρ}^{4.6}$; (5) I S , the stress dominated, intermediate sintering regime, where p = 2 and $f$ ~ $1/\hat{ρ}^{4}$; and (6) L, the late sintering regime, where p = 3 and $f$ ~ 1. At the macroscopic level, the rapid densification and suppression of grain growth observed in the electric field assisted sintering process is a consequence of the compounding effects of the underlying stress-, transport-, and interfacial-energy-induced energy minimization kinetics, as predicted by the multi-scale framework.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Direct Recycling of Lithium-Ion Battery Cathodes: A Multi-Stage Annealing Process to Recover the Pristine Structure and Performance

Direct recycling is an alternative low-cost process that retains the structure of the lithium-ion battery cathode rather than going through materials dissolution and repurification. While the process shows promise, various steps need to be better understood and studied to identify possible roadblocks, cost intensive steps, and needed variations in protocol that may be necessary based on the feedstock of recycled cathodes available. In this study, we have evaluated the process of thermal relithiation as it applies to end-of-life cathode materials. For recovered end-of-life cathodes, approximately 20% of the useable lithium has been lost due to solid electrolyte interface formation, parasitic reactions, and particle isolation; this lost lithium contributes to higher cell impedance and a gradual shift in electrode potentials. As a first step in the direct recycling process, this lithium needs to be restored not only to recover capacity but also to eliminate surface vacancies and hinder surface reconstruction that may increase impedance and impact performance. Here, we have optimized a coating method followed by a two-stage annealing process that restores a model delithiated NMC333 material to pristine performance. Comparisons to single-stage processes are made, and new characterization tools have been used to better understand the processes.

25 ENERGY STORAGE↗
DOE OSTI2026

Hydrogen defects in LaBi 2 O 4 X (X = Cl, Br, and I) Sillén oxyhalide phases and their impacts on ionic transport

Sillén oxyhalides have recently emerged as promising materials for both photocatalytic and ionic transport applications, yet the role of likely-ubiquitous hydrogen-related defects in these layered compounds remains largely unexplored. Here, we employ first-principles defect calculations to investigate incorporation energetics for hydrogen- and oxygen-related defects, as well as their migration barriers in LaBi 2 O 4 X (X = Cl, Br, I) phases. We find that hydrogen interstitials, particularly protonic species (H i + ), are readily accommodated within the open Bi–O layers. Protons compete with oxygen vacancy donors (V O 2+ ) and charge-compensate with oxygen interstitial acceptors (O i 2− ). By linking hydrogen defect formation to water- and oxygen-related redox equilibria, we reveal that V O 2+ facilitates H i + incorporation, while O i 2− promotes interstitial hydroxide formation, establishing a direct connection between proton and oxide-ion transport. Calculated migration barriers indicate that ionic diffusion is confined to Bi–O layers with low barriers of 0.20–0.25 eV for H i + and 0.14–0.25 eV for V O 2+ , suggesting that the materials contain intrinsic pathways for mixed ionic conduction. These results provide a microscopic picture of hydrogen behavior in Sillén oxyhalides and point to design strategies for integrating protonic and oxide-ion transport in layered oxyhalide electrolytes. Band-edge alignment analysis shows that LaBi 2 O 4 I provides the optimal combination of hydrogen solubility, oxygen defect stability, and mixed ionic conductivity, highlighting its potential for low-temperature electrochemical and energy-conversion applications. Overall, this work establishes the defect-driven origin of hydrogen transport in Sillén oxyhalides and expands their applicability beyond photocatalysis to mixed ionic conduction and hydrogen electrochemistry.

Energy - Conversion↗
DOE OSTI2023

Enhancing Photostability of Sn-Pb Perovskite Solar Cells by an Alkylammonium Pseudo-Halogen Additive

High-performance tin-lead perovskite solar cells (PSCs) are needed for all-perovskite-tandem solar cells. However, iodide related fast photodegradation severely limits the operational stability of Sn-Pb perovskites despite the demonstrated high efficiency and thermal stability. Herein, this work employs an alkylammonium pseudo-halogen additive to enhance the power conversion efficiency (PCE) and photostability of methylammonium (MA)-free, Sn-Pb PSCs. Density functional theory (DFT) calculations reveal that the pseudo-halogen tetrafluoroborate (BF 4 - ) has strong binding capacity with metal ions (Sn 2+ /Pb 2+ ) in the Sn-Pb perovskite lattice, which lowers iodine vacancy formation. Upon combining BF 4 - with an octylammonium (OA + ) cation, the PCE of the device with a built-in light-scattering layer is boosted to 23.7%, which represents a new record for Sn-Pb PSCs. The improved efficiency benefits from the suppressed defect density. Under continuous 1 sun illumination, the OABF 4 embodied PSCs show slower generation of interstitial iodides and iodine, which greatly improves the device photostability under open-circuit condition. Moreover, the device based on OABF 4 retains 88% of the initial PCE for 1000 h under the maximum-power-point tracking (MPPT) without cooling.

14 SOLAR ENERGY↗
DOE OSTI2022

Thermodynamically Driven Formation of Intercalated Cu Carpets from Supported Cu Pyramids on MoS 2

Thermodynamic and kinetic analyses based on our first-principles density functional theory calculations are used to interpret the experimentally observed formation of Cu carpets intercalated under the top layer of a 2H-MoS 2 substrate. Spontaneous Cu transport from Cu pyramids on top of the MoS 2 substrate through surface point defects to the growing Cu carpet is shown to be driven by a slightly lower chemical potential for the Cu carpet. We demonstrate that the competition between a preference for a thicker Cu carpet and the cost of elastic stretching of the top MoS 2 layer results in a selected Cu carpet thickness. Furthermore, we also propose that Cu transport occurs primarily via vacancy-mediated diffusion through constricting point defect portals.

36 MATERIALS SCIENCE↗
NASA NTRS1997

Electronic Structure of TlBa2CaCu2O(7-Delta)

The core levels of TlBa2CaCu2O(7-delta) (Tl-1212) epitaxial films have been measured with X-ray photoelectron spectroscopy (XPS). The valence electronic structure has been determined using the full-potential linear muffin-tin-orbital band-structure method and measured with XPS. The calculations show that a van Hove singularity (VHS) lies above the Fermi level (E(sub F)) for the stoichiometric compound (delta = 0.5), while for 50% oxygen vacancies in the Tl-O layer (delta = 0.5) E(sub F) is in close proximity to the VHS. Samples annealed in nitrogen (to reduce the hole overdoping by the removal of oxygen) exhibit higher core-level binding energies and a higher T(sub c), consistent with a shift of E(sub F) closer to the VHS. Comparisons are made to the core levels and valence bands of Tl2Ba2CaCu2O(8 + delta)(Tl-2212) and HgBa2CaCu2O)6 + delta) (Hg- 1212). The similarity of the Cu 2p(sub 3/2) spectra for Tl-1212 and Tl-2212 indicates that the number of Tl-O layers has little effect on the Cu-O bonding. However, the Tl-1212 and Hg-1212 Cu 2p(sub 3/2) signals exhibit differences which suggest that the replacement of T(sup 3+) with Hg(sup 2+) results in a decrease in the O 2p right arrow Cu 3d charge-transfer energy and differences in the probabilities of planar vs apical oxygen charge transfer and/or Zhang-Rice singlet-state formation. Differences between the Tl-1212 and the Tl-2212 and Hg-1212 measured valence bands are consistent with the calculated Cu 3d and (Tl,Hg) 6s/5d partial densities of states.

Vasquez, R. P.↗
DOE OSTI2023

Lithium-compatible and air-stable vacancy-rich Li 9 N 2 Cl 3 for high–areal capacity, long-cycling all–solid-state lithium metal batteries

Attaining substantial areal capacity (>3 mAh/cm 2 ) and extended cycle longevity in all–solid-state lithium metal batteries necessitates the implementation of solid-state electrolytes (SSEs) capable of withstanding elevated critical current densities and capacities. In this study, we report a high-performing vacancy-rich Li 9 N 2 Cl 3 SSE demonstrating excellent lithium compatibility and atmospheric stability and enabling high–areal capacity, long-lasting all–solid-state lithium metal batteries. The Li 9 N 2 Cl 3 facilitates efficient lithium-ion transport due to its disordered lattice structure and presence of vacancies. Notably, it resists dendrite formation at 10 mA/cm 2 and 10 mAh/cm 2 due to its intrinsic lithium metal stability. Furthermore, it exhibits robust dry-air stability. Incorporating this SSE in Ni-rich LiNi 0.83 Co 0.11 Mn 0.06 O 2 cathode-based all–solid-state batteries, we achieve substantial cycling stability (90.35% capacity retention over 1500 cycles at 0.5 C) and high areal capacity (4.8 mAh/cm 2 in pouch cells). These findings pave the way for lithium metal batteries to meet electric vehicle performance demands.

25 ENERGY STORAGE↗