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At least 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Structure and Electrochemical Properties of Bronze Phase Materials Containing Two Transition Metals

Bronze phase transition-metal oxides have recently attracted attention as high-rate lithium-ion battery anode materials. Their crystal structures are distinguished by large tunnels and an open framework, facilitating lithium-ion diffusion and high-rate charge–discharge properties. The presence of two transition metals also offers a route to achieve high energy density from multielectron redox. In this paper, we report the chemistry, structure, and electrochemical properties of two different bronze phase compositions having the same stoichiometry: W 3 Nb 2 O 14 and Mo 3 Nb 2 O 14 . These materials provide insight into how the transition metals affect the electrochemical behavior and structural stability of bronze phase materials. Mo 3 Nb 2 O 14 exhibits greater than 1 electron redox per transition metal leading to lithium capacities above 200 mAh g –1 at C/2 but is unable to maintain this high capacity at high rates due to incomplete Mo redox reactions. In contrast, W 3 Nb 2 O14 exhibits reversible redox reactions and retains its open structure on cycling. This study highlights the potential of bronze phase materials containing two transition metals to exhibit fast charging properties with a high energy density.

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

Phase transition to blob-hole coherent structure in the Hasegawa–Mima model for plasmas

An equilibrium statistical mechanics theory for the Hasegawa–Mima equations of toroidal plasmas, with canonical constraint on energy and microcanonical constraint on potential enstrophy, is solved exactly as a spherical model. The use of a canonical energy constraint instead of a fixed-energy microcanonical approach is justified by the preference for viewing real plasmas as an open system. A significant consequence of the results obtained from the partition function, free energy and critical temperature, is the condensation into a ground state exhibiting a blob-hole-like structure observed in real plasmas.

Physics↗
DOE OSTI2023

Strain effects on stability of topological ferroelectric polar configurations in (PbTiO3) n /(SrTiO3) n superlattices

The (PbTiO3)n/(SrTiO3)n (PTO/STO) superlattice system has been shown to exhibit interesting topological phases (e.g., vortices and skyrmions) in addition to normal ferroelectric domain states. Existing studies are mostly focused on the dependence of topological polar distributions and properties of PTO/STO superlattice on its periodicity. Here, we study the strain effect on the topological phase transitions and ferroelectric domain structures employing phase-field simulations. We summarized in an isotropic strain (in-plane misfit strain along the x direction is equal to that along the y direction) periodicity phase diagram displaying the stability regions of different polar topological states, including normal ferroelectric twins, vortices, skyrmions, and mixtures of vortices and twins. We also analyzed the polarization configurations under anisotropic in-plane strains (in-plane misfit strain along the x direction is not equal to that along the y direction) and demonstrated that the strain anisotropy can be used to tune the directions of vortex arrays along either the [100] pc or [010] pc directions or labyrinth vortex arrays. This work offers guidance to manipulating polar structures in the PTO/STO superlattices via strain engineering.

Physics↗
DOE OSTI2023

Machine Learning Reveals Memory of the Parent Phases in Ferroelectric Relaxors Ba(Ti$_{1-x}$,Zr x )O 3

Machine learning has been establishing its potential in multiple areas of condensed matter physics and materials science. Here, in this work, an unsupervised machine learning workflow is developed and used within a framework of first-principles-based atomistic simulations to investigate phases, phase transitions, and their structural origins in ferroelectric relaxors, Ba(Ti 1-x ,Zr x )O 3 . The applicability of the workflow is first demonstrated to identify phases and phase transitions in the parent compound, a prototypical ferroelectric BaTiO 3 . Then the workflow is applied for Ba(Ti 1-x ,Zrx)O 3 with x ≤ 0.25 to reveal i) that some of the compounds bear a subtle memory of BaTiO 3 phases beyond the point of the pinched phase transition, which could contribute to their enhanced electromechanical response; ii) the existence of peculiar phases with delocalized precursors of nanodomains—likely candidates for the controversial polar nanoregions; and iii) nanodomain phases for the largest concentrations of x.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Local structure of Mott insulating iron oxychalcogenides La 2 O 2 Fe 2 OM2(M=S,Se)

Here, we describe the local structural properties of the iron oxychalcogenides, La 2 O 2 Fe 2 OM 2 (M=S,Se), by using pair distribution function analysis applied to total scattering data. Our results from neutron powder diffraction show that M = S and Se possess similar nuclear structures at low and room temperatures. The local crystal structures were studied by investigating deviations in atomic positions and the extent of the formation of orthorhombicity. Analysis of the total scattering data suggests that buckling of the Fe 2 O plane occurs below 100 K. The buckling may occur concomitantly with a change in octahedral height. Furthermore, within a typical range of 1-2 nm, we observed a short-range orthorhombiclike structure suggestive of nematic fluctuations in both of these materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Ultrafast formation of a transient two-dimensional diamondlike structure in twisted bilayer graphene

Due to the absence of matching carbon atoms at honeycomb centers with carbon atoms in adjacent graphene sheets, theorists predicted that a sliding process is needed to form AA, AB', or ABC stacking when directly converting graphite into sp 3 bonded diamond. Here, using twisted bilayer graphene, which naturally provides AA and AB' stacking configurations, we report the ultrafast formation of a transient two-dimensional diamondlike structure (which is not observed in aligned graphene) under femtosecond laser irradiation. This photoinduced phase transition is evidenced by the appearance of bond lengths of 1.94 and 3.14 Å in the time-dependent differential pair distribution function using MeV ultrafast electron diffraction. Molecular dynamics and first-principles calculation indicate that sp 3 bonds nucleate at AA and AB' stacked areas in a moiré pattern. This work sheds light on the direct graphite-to-diamond transformation mechanism, which has not been fully understood for more than 60 years.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

An isolated water droplet in the aqueous solution of a supramolecular tetrahedral cage

Water under nanoconfinement at ambient conditions has exhibited low-dimensional ice formation and liquid–solid phase transitions, but with structural and dynamical signatures that map onto known regions of water’s phase diagram. Using terahertz (THz) absorption spectroscopy and ab initio molecular dynamics, we have investigated the ambient water confined in a supramolecular tetrahedral assembly, and determined that a dynamically distinct network of 9 ± 1 water molecules is present within the nanocavity of the host. The low-frequency absorption spectrum and theoretical analysis of the water in the Ga 4 L 6 12– host demonstrate that the structure and dynamics of the encapsulated droplet is distinct from any known phase of water. A further inference is that the release of the highly unusual encapsulated water droplet creates a strong thermodynamic driver for the high-affinity binding of guests in aqueous solution for the Ga 4 L 6 12– supramolecular construct.

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

Equation of state, phase transitions, and band-gap closure in Pb Cl 2 and Sn Cl 2

The equations of state and band-gap closures for Pb Cl 2 and Sn Cl 2 were studied using both experimental and theoretical methods. Here we measured the volume of both materials to a maximum pressure of 70 GPa using synchrotron-based angle-dispersive powder x-ray diffraction. The lattice parameters for both compounds showed anomalous changes between 16–32 GPa, providing evidence of a phase transition from the cotunnite structure to the related Co 2 Si structure, in contrast to the postcotunnite structure as previously suggested. First-principles calculations confirm this finding and predict a second phase transition to a Co 2 Si-like structure between 75– 110 GPa in Pb Cl 2 and 60–75 GPa in Sn Cl 2 . Band gaps were measured under compression to ~70 GPa for Pb Cl 2 and ~66 GPa for Sn Cl 2 and calculated up to 200 GPa for Pb CI 2 and 120 GPa for Sn Cl 2 . We find an excellent agreement between our experimental and theoretical results when using the Heyd-Scuseria-Ernzerhof (HSE06) hybrid functional, which suggests that this functional could reliably be used to calculate the band gap of similar AX 2 compounds. Experimental and calculated band-gap results show discontinuous decreases in the band gap corresponding to phase changes to higher-coordinated crystal structures, giving insight into the relationship between interatomic geometry and metallicity.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Direct Observation of Electron Beam-Induced Phase Transition in MgCrMnO 4

Irreversible structural transformation in intercalation-type cathode materials, which has been frequently observed, has been perceived as a principal cause of capacity fading and voltage decay in (uni) multivalent batteries. Herein, we explored the electron beam-induced spinel to defective rocksalt phase transitions in MgCrMnO 4 , a potential multivalent cation intercalation cathode, using atomic-resolution imaging and spectroscopy in an aberration-corrected scanning transmission electron microscope. This dynamic electron beam irradiation study of specific structural transformations provides an atomistic understanding of the structural evolution observed in transition-metal oxide spinels during electrochemical cycling using multivalent cations, such as Mg 2+ . By combining an imaging study with first-principles modeling, we demonstrate that the mechanism of the spinel to defective rocksalt transformation in MgCrMnO 4 nanostructures is enabled by the presence of oxygen vacancies and is, therefore, very similar to that observed in transition-metal oxide spinels upon Li intercalation.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Photoinduced reversible phase transition in a phenothiazine-based metal-organic framework

Photoinduced phase transitions in metal-organic frameworks are provoked by structural changes of photoresponsive linkers within the framework under light irradiation. These transitions are rare but fundamentally important as they can bring about light-switchability on a variety of properties of the materials. In this work, phenothiazine as a photoresponsive unit with distinctive photochemical properties is incorporated into a Zn-based metal-organic framework, PCN-401. The structural characterization of PCN-401 revealed a reversible structural transition upon light irradiation. The mechanisms behind the photoinduced phase transition are studied systematically by spectrometric methods and structural stability characterization. Our mechanistic studies successfully showcased how the phenothiazine unit in the framework undergoes structural transformation under light irradiation and how the reversible phase transition leads to the property changes. The findings have emphasized the significance of phenothiazine in photoresponsive materials and can serve as inspiration for the design and understandings of next-generation photoresponsive metal-organic materials.

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

Controlling Interlayer Disorder Toward Reversible Phase Transition in a Layered Sodium Manganese Oxide Cathode

Sodium manganese oxides are promising Na-ion battery cathodes but they suffer from irreversible phase transitions during electrochemical reactions. Most strategies to date have aimed to suppress the phase transitions by stabilizing their layered structures through limiting the content of extractable Na + . Here, we conversely increase atomic disorder in the Na-birnessite, a layered sodium manganese oxide, and thereby modulate its phase transition behavior toward improved electrochemical reversibility. Our study reveals that Mn vacancies and Mn migrated into the interlayer affect interlayer local environment of Na + and water molecules consequently enhancing Na + mobility. We observe better capacity retention for disordered “D-Na-birnessite”, which undergoes a reversible phase transition from the birnessite-type structure to an O′3-type α-Na x MnO 2 -like structure through another intermediate metastable birnessite-type phase. In conclusion, this research highlights the positive effects of atomic disorder to regulate phase transition routes for achieving superior electrochemical reversibility, finally paving the way to overcoming the limits of layered oxide cathodes.

Kang, Seongkoo [Korea Univ., Seoul, (Korea, Republ↗
DOE OSTI2024

Oxygen redox activities governing high-voltage charging reversibility of Ni-rich layered cathodes

A schematic illustration indicative of the improved structural reversibility through stabilizing oxidized oxygen by Al doping. The chemical reactions and phase transitions at high voltages are generally considered to determine the electrochemical properties of high-voltage layered cathodes such as Ni-rich rhombohedral oxides. Even if significantly higher SOCs (states-of-charge) are utilized above the capability of transition metal redox (primarily Ni and Co), the effect of oxygen redox on Ni-rich rhombohedral oxides still looks mysterious thereby necessitating research that can clarify the relationship between redox reactions and phase transitions. Here, we performed a comprehensive and comparative study of the cationic and anionic redox reactions, as well as the structural evolution of a series of commercial Ni-rich layered oxides with and without Al doping. We combined the results from X-ray spectroscopy, operando electrochemical mass spectrometry, and neutron diffraction with electrochemical properties and thereby revealed the different oxygen redox activities associated with structural and electrochemical degradations. We reveal that Al doping suppresses the irreversible oxygen release but enhances the lattice oxygen oxidization. With this modulated oxygen redox activity, the Ni-rich layered oxides’ notorious H2–H3 structural phase transition becomes highly reversible. Our findings disentangle the different oxygen redox activities during high-voltage cycling and clarify the role of dopants in the Ni-rich layered oxides in terms of structural and electrochemical stability, shedding light on the future direction of optimizing layered cathode materials for safer high energy-density secondary batteries.

Lee, Gi-Hyeok↗
DOE OSTI2024

Optical pulse-induced ultrafast antiferrodistortive transition in SrTiO 3

The ultrafast dynamics of the antiferrodistortive phase transition in perovskite SrTiO 3 is monitored via time-domain Brillouin scattering. Using femtosecond optical pulses, we initiate a thermally driven tetragonal-to-cubic structural transformation and detect the crystal phase through changes in the frequency of Brillouin oscillations (BO) induced by propagating acoustic phonons. Coupling the measured BO frequency with a spatiotemporal heat diffusion model, we demonstrate that, for a sample kept in the tetragonal phase, deposition of sufficient thermal energy induces a rapid transformation of the heat-affected region to the cubic phase. The initial phase change is followed by a slower reverse cubic-to-tetragonal phase transformation occurring on a timescale of hundreds of picoseconds. Here, we attribute this ultrafast phase transformation in the perovskite to a structural resemblance between atomic displacements of the R-point soft optic mode of the cubic phase and the tetragonal phase, both characterized by anti-phase rotation of oxygen octahedra. The structural relaxation time exhibits a strong temperature dependence consistent with the prediction of the equation of motion describing collective oxygen octahedra rotation based on the energy landscape of the phenomenological Landau theory of phase transitions. Evidence of such a fast structural transition in perovskites can open up new avenues in information processing and energy storage sectors.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Structural Stabilization of P2-type Sodium Iron Manganese Oxides by Electrochemically Inactive Mg Substitution: Insights of Redox Behavior and Voltage Decay

Layered P2-type Na 0.8 Mn 0.5 Fe 0.5 O 2 cathode material is a promising candidate for next-generation sodium-ion batteries due to the economical and environmentally benign characteristics of Mn and Fe. The poor cycling stability of the material, however, is still a problem that must be solved. To address the problem, here, electrochemically inactive Mg 2+ was introduced into the structure by substituting some of the Fe ions. It was shown that Mg substitution led to a smoother voltage profile with improved cycling performance and rate capability. These observations were attributed to the suppressed structural changes during electrochemical processes. Detailed redox mechanisms, associated local structural changes, and phase transitions were investigated by X-ray absorption spectroscopy and X-ray diffraction. From the detailed analysis of electrochemical behaviors, it was also identified how the redox reactions and structural disordering occurred in the high-and low-voltage regions and how Mg substitution stabilized the structure.

25 ENERGY STORAGE↗
NASA NTRS1994

The phenomenological status of late time phase transition models after cosmic background radiation anisotropy measurements

Some relatively model-independent results for structure formation via late time phase transitions (LTPT) are discussed. In particular, generic LTPT power spectra are presented. The implication of the recent Cosmic Background Explorer (COBE) detection of the cosmic background radiation (CBR) anisotropy at large angular scales (greater than or approximately equal to 7 deg) and the tight upper limits from small angular scales (approximately 1 deg) to LTPT models are discussed. Special attention is focused on the observational constraints and possible non-Gaussian signatures of CBR temperature anisotropies from LTPT and other non-Gaussian models. It is shown that while LTPT have been seriously constrained by the recent data, viable models do remain which provide more power on the 100-200 Mpc scales than do more traditional primordial Gaussian density fluctuation models. Tests for such models are presented, including possible anisotropies on angular scales less than 8 min.

Luo, Xiaochun↗
DOE OSTI2022

Quantum simulation of quantum phase transitions using the convex geometry of reduced density matrices

Transitions of many-particle quantum systems between distinct phases at absolute-zero temperature, known as quantum phase transitions, require an exacting treatment of particle correlations. Here in this work, we present a general quantum-computing approach to quantum phase transitions that exploits the geometric structure of reduced density matrices. While typical approaches to quantum phase transitions examine discontinuities in the order parameters, the origin of phase transitions—their order parameters and symmetry breaking—can be understood geometrically in terms of the set of two-particle reduced density matrices (2-RDMs). The convex set of 2-RDMs provides a comprehensive map of the quantum system including its distinct phases as well as the transitions connecting these phases. Because 2-RDMs can potentially be computed on quantum computers at nonexponential cost, even when the quantum system is strongly correlated, they are ideally suited for a quantum-computing approach to quantum phase transitions. We compute the convex set of 2-RDMs for a Lipkin-Meshkov-Glick spin model on IBM superconducting-qubit quantum processors. Even though computations are limited to few-particle models due to device noise, comparisons with a classically solvable 1000-particle model reveal that the finite-particle quantum solutions capture the key features of the phase transitions including the strong correlation and the symmetry breaking.

74 ATOMIC AND MOLECULAR PHYSICS↗