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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 649 records · Page 36
All sourcesNASA NTRSDOE OSTI
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 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 OSTI2022

Controlling the Phase Transition in CsPbI 3 Nanowires

Cesium lead iodide (CsPbI 3 ) is a promising semiconductor with a suitable band gap for optoelectronic devices. CsPbI 3 has a metastable perovskite phase that undergoes a phase transition into an unfavorable nonperovskite phase in an ambient environment. This phase transition changes the optoelectronic properties of CsPbI 3 and hinders its potential for device applications. Therefore, it is of central importance to understand the kinetics of such instability and develop strategies to control and stabilize the perovskite phase. Here, we use ultralong CsPbI 3 nanowires as a model platform to investigate the phase transition kinetics. Our results depict the role of environmental stressors (moisture and temperature) in controlling the phase transition dynamics of CsPbI 3 , which can serve as guiding principles for future phase transition studies and the design of related photovoltaics. Furthermore, we demonstrate the controllability of phase propagation on individual nanowires by varying the moisture level and temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Thermodynamics of grain-boundary phases

The past decade has seen a significant increase in research efforts aimed at understanding the thermodynamics of low-dimensional phases existing in many materials systems, ranging from two-dimensional materials to core regions of extended defects in crystalline solids. We review the current status of theoretical, computational, and experimental research on the “defect phases,” focusing on grain boundaries (GBs) in elemental and multicomponent polycrystalline materials. After reviewing the generalized concept of a phase of any dimensionality, we discuss recent progress in atomistic computer simulations of GB phase transformations and phase coexistences, including the observation of one-dimensional defects separating GB phases (defects in defects). Computational predictions compare well with experimental observations of multiple GB phases and segregation-induced phase transformations. An intriguing open question of GB thermodynamics is whether the GB free energy can be driven to a zero value by increasing solute segregation. We review recent efforts to understand this ultimate thermodynamic stabilization of GB phases and the possible polycrystalline microstructures that may arise. An outlook for future research in the field is discussed.

Materials science↗
DOE OSTI2025

Fermilab PIP-II Master Oscillator and Precision Reference Line Design and Construction

The phase averaging reference line system pro- vides the RF phase reference, LO and clock sig- nals to the LLRF and other accelerator sub- systems. The PIP-II linac has RF systems at three frequencies – 162.5 MHz, 325 MHz and 650 MHz. A temperature-stabilized, low-phase- noise oscillator is used as the master oscil- lator. Phase reference signals at 162.5 MHz, 325 MHz, and 650 MHz, along with LO signals at 182.5 MHz, 345 MHz, 670 MHz and LLRF clocks at 1320 MHz and 1300 MHz, are generated in temperature-controlled RF modules at each fre- quency section. A phase reference from each module travels to the next section, where it is doubled to produce required frequencies. The reference also travels alongside the accelerating cavities in the tunnel, allowing cavity probe and reference cables to temperature track and reduce measurement errors from temperature changes or phase drift.

Syed, Ahmed [Fermilab]↗
DOE OSTI2025

Master Oscillator and Phase Reference Line Design for the PIP-II Linac

The phase averaging reference line system provides the RF phase reference, LO and clock signals to the LLRF and other accelerator sub-systems. The PIP-II linac has RF systems at three frequencies - 162.5 MHz, 325 MHz and 650 MHz. A temperature-stabilized, low-phase-noise oscillator is used as the master oscillator. Phase reference signals at 162.5 MHz, 325 MHz, and 650 MHz, along with LO signals at 182.5 MHz, 345 MHz, 670 MHz and LLRF clocks at 1320 MHz and 1300 MHz, are generated in temperature-controlled RF modules at each frequency section. A phase reference from each module travels to the next section, where it is doubled to produce required frequencies. The reference also travels alongside the accelerating cavities in the tunnel, allowing cavity probe and reference cables to temperature track and reduce measurement errors from temperature changes or phase drift.

Syed, A. [Fermilab]↗
DOE OSTI2020

Doping effect of Al in LLZO

Lithium ion batteries have become a common use in most electronic devices and transportation. However, the use of liquid electrolytes poses a serious safe hazard due to their high flammability. The narrow operating temperature and voltage windows also limit further improvement of the energy density.Solid-state lithium batteries with the use of more stable and safer solid electrolyte have garnered much attention and could be the future choice for battery technology. A promising potential candidate for the solid electrolyte component is the garnet type Li 7 La 3 Zr 2 O 12 (LLZO) ceramic material since it possesses high ionic conductivity at room temperature and enables the use of high capacity lithium anode and high voltage/capacity cathodes.However, to form the stable cubic phase of LLZO and high densification,high sintering temperatures above 1100°C is typically required, which causes Lithium loss of the system.Many studieshave been taken to dop LLZO with various precursors such as Ga, Ta, and Al to stabilize the cubic structure and reduce calcination temperature, while the doping effect on sintering densification is still unclear. In this study Al doping along with ball milling were explored to stabilize the cubic phase of LLZO and improve densification, while reducing the amount of impurity phases. Samples were synthesized from the precursors Li 2 CO 3 , Al 2 O 3 , La 2 O 3 , and ZrO 2 by ball milling followed by heat treatment for 12 hours at 1000°C. XRD with Rietveld fitting was used to determine the two phases of LLZO (cubic, tetragonal) and other possible secondary phases. Furthermore,SEM with top and cross sectional views was conducted to investigate the morphology and microstructure of sintered pellets.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Observation of spontaneous ferromagnetism in a two-dimensional electron system

Significance Ground states of low-disorder, interacting, dilute electron systems are of fundamental interest in understanding electron–electron interaction phenomena. Our experimental data on a clean two-dimensional electron system reveal a sequence of transitions as the density is lowered. Starting from high densities, we observe a transition from a metallic state to an exotic insulating phase that is stabilized by disorder and interaction. As we further lower the density, we observe signs of a spontaneous transition to a ferromagnetic ground state and then to a strongly insulating state whose characteristics suggest that it is a pinned solid phase, possibly a (ferromagnetic) Wigner solid. We also find that the onset of ferromagnetism can be controlled by tuning the electrons’ valley degree of freedom.

2D electron system↗
DOE OSTI2023

Decoding Zeolite Crystallization and Stage III in Nuclear Waste Glasses by Coupled Modeling and Experiments

Under specific conditions of pH and temperature, nuclear waste immobilization borosilicate glasses may exhibit a sudden acceleration in their corrosion kinetics (stage III)—a behavior that has been associated with the formation of zeolite crystals. Such accelerated dissolution may compromise the integrity of nuclear wasteforms placed in geological depositories. However, thus far, none of the available models is able to predict the thermodynamic propensity and kinetics of zeolite precipitation as a function of the solution conditions due to (i) a lack of fundamental knowledge regarding the nucleation & growth mechanisms of zeolitic phases, (ii) uncertainty regarding the compositions (types) of zeolites that may form and the rate-limiting step in their precipitation as a function of the solution conditions, and (iii) the complexities that arise due to the vast parametric space (i.e., solution chemistry, temperature, number of secondary phases, etc.) that encompass these systems under conditions of environmental exposure. To resolve these challenges, this project aimed to unambiguously identify the thermodynamic propensity for zeolite precipitation and the kinetics thereof as a function of the solution conditions (composition, pH, and temperature). To achieve this goal: 1) We identified the solution conditions and zeolite phases relevant to nuclear glass dissolution. 2) We performed a series of ab initio molecular dynamics (AIMD) simulations to compute the thermodynamic properties of a group of characteristic zeolites that features a large range of compositions, various hydration levels, a wide range of framework structures, and partial atomic site occupancies. 3) We released a first-of-a-kind self-consistent thermodynamic database that can be used to assess the kinetics and the stability fields of zeolitic phases within a Gibbs energy minimization (GEM) framework. 4) We developed a robust geochemical modeling method allowing us to predict the stability of secondary phases (including zeolites, calcium–silicate–hydrate gels, and clays) upon the dissolution of nuclear waste immobilization glasses. 5) We introduced a model that predicts the dissolution kinetics of a series of borosilicate nuclear waste immobilization glasses in terms of the topology of their atomic network. 6) We investigated the roles of the solution composition on the crystallization kinetics of phillipsite zeolites and tobermorite silicate hydrates. Via PNNL’s collaboration and engagement, this project directly supports DOE’s nuclear waste immobilization activities by offering a technical, science-based foundation that will (i) facilitate predictions of the long-term corrosion rates and extents of existing nuclear waste immobilization glasses to help ensure safe and successful vitrification operations, (ii) inform the development of advanced glass formulations with enhanced durability, and, (iii) enable cost-savings that result from making more decisive and hence less conservative predictions while offering higher levels of nuclear waste embedment in smaller, more compact glass volumes.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2026

Phase instability-coupled fracture behavior in garnet LLZO solid electrolytes: a machine learning-enabled atomistic study

Fracture in the garnet-type solid electrolyte Li 7 La 3 Zr 2 O 12 (LLZO) poses a critical threat to both the performance and safety of solid-state batteries. To unravel the coupled chemomechanical processes that govern fracture in LLZO under external loading, we carry out large-scale molecular-dynamics simulations with a validated machine-learning force field. Our results demonstrate that triaxial stresses at crack flanks trigger a localized cubic-to-tetragonal phase transformation, which is accompanied by Li-ion rearrangement. The emergent tetragonal domains feature lattice contraction normal to the fracture plane, imposing coherent misfit strains that provide an additional driving force for further crack propagation. Crucially, introducing Li deficiencies stabilizes the cubic phase, postponing the phase transition and thereby delaying fracture initiation. These findings highlight the role of intrinsic phase instability in dictating LLZO's fracture resistance and its critical connection to local Li concentration. This chemomechanical coupling points toward targeted strategies to enhance the mechanical robustness of garnet electrolytes, including tuning Li content, ensuring dopant homogeneity, and refining processing protocols.

Materials science↗
DOE OSTI2025

Nanoscale Strain and Octahedral Tilting Removes Structural and Nonradiative Defects in 2D-Templated FAPbI 3

The halide perovskite formamidinium lead iodide (FAPbI 3 ) is a prime candidate for photovoltaics due to its excellent optoelectronic properties, but its application has been limited due to its structural instability. The large size of the FA cation results in metastability of the photoactive cubic phase and a facile degradation into thermodynamically stable hexagonal phases at room temperature. Recently, the incorporation of two-dimensional (2D) Ruddlesden-Popper halide perovskite seeds into a FAPbI 3 precursor solution was shown to template the growth of and stabilize cubic FAPbI 3 . Here, in this study, we investigate the nanoscale structural and optoelectronic mechanisms behind the observed bulk stabilization using synchrotron-based X-ray microscopies. Nanoprobe X-ray diffraction reveals 2D-templated FAPbI 3 films exhibit an average compressive strain normal to the substrate of -3.3%, 2-fold larger than that of MACl-stabilized FAPbI 3 . This compression creates locally templated regions composed of tetragonal-phase FAPbI 3 distributed nonuniformly throughout the film with fewer crystalline defects than purely cubic regions. Scanning X-ray excited optical luminescence (X-ray analog of photoluminescence) reveals that this local templating results in increased radiative recombination and red-shifted band edge and emission. Our results provide insight into the microscopic mechanism for the phase stabilization of FAPbI 3 using 2D perovskites as templates.

X-ray diffraction↗
DOE OSTI2021

Charge density wave and superconductivity in the disordered Holstein model

The interplay between electron-electron correlations and disorder has been a central theme of condensed matter physics over the past several decades, with particular interest in the possibility that interactions might cause delocalization of an Anderson insulator into a metallic state, and the disrupting effects of randomness on magnetic order and the Mott phase. In this work, we extend this physics to explore electron-phonon interactions and show, via exact quantum Monte Carlo simulations, that the suppression of the charge density wave correlations in the half-filled Holstein model by disorder can stabilize a superconducting phase. Our simulations thus capture qualitatively the suppression of charge ordered phases and emergent superconductivity recently seen experimentally.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Stabilizing the heavily-doped and metallic phase of MoS 2 monolayers with surface functionalization

Monolayer molybdenum disulfide (MoS 2 ) is one of the most studied two-dimensional (2D) transition metal dichalcogenides that is being investigated for various optoelectronic properties, such as catalysis, sensors, photovoltaics, and batteries. One such property that makes this material attractive is the ease in which 2D MoS 2 can be converted between the semiconducting (2H) and metallic/semi-metallic (1T/1T') phases or heavily n-type doped 2H phase with ion intercalation, strain, or excess negative charge. Using n-butyl lithium (BuLi) immersion treatments, we achieve 2H MoS 2 monolayers that are heavily n-type doped with shorter immersion times (10–120 mins) or conversion to the 1T/1T' phase with longer immersion times (6–24 h); however, these doped/converted monolayers are not stable and promptly revert back to the initial 2H phase upon exposure to air. To overcome this issue and maintain the modification of the monolayer MoS 2 upon air exposure, we use BuLi treatments plus surface functionalization p-(CH 3 CH 2 ) 2 NPh-MoS 2 (Et 2 N-MoS 2 )—to maintain heavily n-type doped 2H phase or the 1T/1T' phase, which is preserved for over two weeks when on indium tin oxide or sapphire substrates. We also determine that the low sheet resistance and metallic-like properties correlate with the BuLi immersion times. These modified MoS 2 materials are characterized with confocal Raman/photoluminescence, absorption, x-ray photoelectron spectroscopy as well as scanning Kelvin probe microscopy, scanning electrochemical microscopy, and four-point probe sheet resistance measurements to quantify the differences in the monolayer optoelectronic properties. We will demonstrate chemical methodologies to control the modified monolayer MoS 2 that likely extend to other 2D transition metal dichalcogenides, which will greatly expand the uses for these nanomaterials.

2D TMDC↗
DOE OSTI2026

The impact of metastability on the high-pressure behavior of cerium

The structures adopted by solids under pressure are often assumed to reflect thermodynamic equilibrium, yet in many materials phase selection is strongly influenced by kinetic pathways and microstructural inheritance. Elemental cerium (Ce) exemplifies this challenge, with decades of conflicting reports describing different high-pressure crystal structures emerging under nominally identical conditions. Here we use neutron diffraction from large ( ~ 60 mm 3 ) sample volumes to follow the structural evolution in ultra-high-purity Ce during controlled pressure-temperature cycling between 85 and 295 K and up to 8 GPa. We find that the crystal structure formed at high pressure depends on the compression pathway: slow compression ( ~ 0.25 GPa hr −1 ) at room temperature favors an orthorhombic phase (α'), whereas slow ( ~ 0.25 GPa hr −1 ) and also moderately faster ( ~ 0.5 GPa hr −1 ) compression at low temperature stabilizes a pure monoclinic phase (α"). The low-temperature phase persists metastably over a wide temperature range but transforms irreversibly upon heating above ~ 280 K, or modest pressure cycling. Remarkably, the lower-pressure γ phase remains trapped far beyond the expected stability field, persisting to the highest pressures studied. These observations show that phase selection in Ce is governed by kinetics and microstructural memory rather than equilibrium thermodynamics or sample morphology alone, establishing path dependence as a defining feature of its high-pressure behavior.

Ridley, Christopher J. [Oak Ridge National Laborat↗
DOE OSTI2024

Frank–Kasper Phases of Diblock Copolymer Melts: Self-Consistent Field Results of Two Commonly Used Models

We constructed phase diagrams of conformationally asymmetric diblock copolymer A-B melts using the polymer self-consistent field (SCF) calculations of both the dissipative particle dynamics chain (DPDC) model (i.e., compressible melts of discrete Gaussian chains with the DPD non-bonded potential) and the “standard” model (i.e., incompressible melts of continuous Gaussian chains with the Dirac δ-function non-bonded potential) in the χN-ε plane, where χN and ε characterize, respectively, the repulsion and conformational asymmetry between the A and B blocks, at the A-block volume fraction f = 0.2 and 0.3. Consistent with previous SCF calculations of the “standard” model, σ and A15 are the only stable Frank–Kasper (FK) phases among the five FK (i.e., σ, A15, C14, C15 and Z) phases considered. The stability of σ and A15 is due to their delicate balance between the energetic and entropic contributions to the Helmholtz free energy per chain of the system, which, within our parameter range, increases in the order of σ/A15, Z, and C14/C15. While in general the SCF phase diagrams of these two models are qualitatively consistent, A15 is not stable for the DPDC model at the copolymer chain length N = 10 and f = 0.3; any differences in the SCF phase diagrams are solely due to the differences between these two models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Effects of substitutional Ga on the phonons of δ -phase Pu based on density functional theory calculations

The delta phase of Pu is stabilized by Ga doping, but the mechanism of this stabilization remains an open question. Density functional theory calculations focused on how Ga doping affects the phonons sheds some light on the phonons' contribution to the stabilization. Here, the calculated phonon modes of Ga-doped delta phase Pu fall into two distinct types: localized, high frequency Ga-dominated phonon modes, and Pu-dominated modes at lower frequencies. Increasing the Ga concentration has an effect on the Pu-dominated phonon modes opposite to that of compression: higher-frequency modes soften, and lower-frequency modes stiffen. The latter provides an indication that the stabilization mechanism is not due to a thermodynamic contribution from the phonons. Furthermore, the stiffened phonon modes include candidate modes that describe possible pathways into low-temperature phases, suggesting that doping with Ga could impede such pathways.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

Electronic glasses from a broken gauge symmetry in disorder-free systems

Glass phases can be stabilized by quenched disorders, as in most spin-glass materials, or self-generated through kinetic freezing in disorder-free systems. A canonical example of the latter is structural glasses, which have been extensively studied for many decades. Yet, how the rugged energy landscape of a glass phase is spontaneously generated in disorder-free systems remains one of the key questions in glass physics. Here, in this work, we present a general electronic mechanism for the emergence of glassy phase using the example of itinerant electrons coupled to XY spins on a lattice. This model can also be viewed as the mean-field theory of a superconducting system with attractive density-density interactions. Intriguingly, the electron gauge symmetry in the strong pairing limit gives rise to a macroscopic degeneracy of XY spins. In the presence of electron hopping that breaks the gauge symmetry, the lifting of the extensive degeneracy leads to a glass phase with disordered pairings. Our findings highlight a scenario in which a glassy state originates from the breaking of quantum gauge symmetry without quenched disorders.

XY model↗
DOE OSTI2023

Magnetism and T-x phase diagrams of Na- and Ag-substituted EuCd 2 As 2

EuCd 2 As 2 is an antiferromagnetic semimetal, that can host non-trivial topological properties, depending upon its magnetic state and excitations. Here, we report the synthesis and characterization of Eu(Cd 1-x Ag x ) 2 As 2 and Eu 1-y Na y Cd 2 As 2 , and study the evolution and nature of magnetic order with doping. Temperature-substitution phase diagrams are constructed from the electrical resistance and magnetic susceptibility data. We observe a splitting of the magnetic transition into two different transitions, and the gradual increase in one of the transition temperatures with Agand Na-substitution. The other transition remains more or less independent of doping. Further, we show that a magnetic state with a net ferromagnetic moment is stabilized by both Ag and Na doping and this can be explained by considering the changes in band filling due to substitution as suggested by density functional theory (DFT) calculations. We thus show that chemical substitution and the subsequent changes in band filling could be a pathway to tune the magnetic ground state and to stabilize a ferromagnetic phase in EuCd 2 As 2 .

36 MATERIALS SCIENCE↗