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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 1,153 records · Page 64
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Li 2.9 Fe 0.9 Zr 0.1 Cl 6 as Redox-Active Catholyte for Solid-State Li-Ion Batteries

Solid electrolytes are one of the key challenges that hinder the commercialization of all-solid-state batteries. Most efforts have been made to advance the development of solid electrolytes as separators, while the development of catholytes, particularly redox-active catholytes, has been less extensively studied. The high loading of catholytes in composite cathodes, while facilitating ionic conduction, drastically decreases the energy density of the battery. Here, we report an alternative strategy to improve the energy density by using Li 2.9 Fe 0.9 Zr 0.1 Cl 6 as a redox-active catholyte. With a composite cathode containing uncoated LiCoO2 and Li 2.9 Fe 0.9 Zr 0.1 Cl 6 , the solid-state cell not only shows excellent rate capability and stable long-term cycling, benefiting from the high ionic conductivity of Li 2.9 Fe 0.9 Zr 0.1 Cl 6 , but also shows a high cathode specific capacity of ~153 mAh·g –1 . This study broadens the chemical space of the materials design for lithium-ion conductors with redox-active elements (e.g., Fe, Ti, V, and Cr), offering new opportunities to reduce the cost and improve the energy density for all-solid-state batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Sensitivity-Enhanced 207 Pb Solid-State NMR Spectroscopy for the Rapid, Non-Destructive Characterization of Organolead Halide Perovskites

Here, organolead halide and mixed halide perovskites (CH 3 NH 3 PbX 3 , CH 3 NH 3 PbX 3– n Y n , X and Y = Cl – , Br – , or I – ) are promising materials for photovoltaics and optoelectronic devices. 207 Pb solid-state NMR spectroscopy has previously been applied to characterize phase segregation and halide ion speciation in mixed halide perovskites. However, NMR spectroscopy is an insensitive technique that often requires large sample volumes and long signal averaging periods. This is especially true for mixed halide perovskites, which give rise to extremely broad 207 Pb solid-state NMR spectra. Here, we quantitatively compare the sensitivity of the various solid-state NMR techniques on pure and mixed halide organolead perovskites and demonstrate that both fast MAS and DNP can provide substantial gains in NMR sensitivity for these materials. With fast MAS and proton detection, high signal-to-noise ratio two-dimensional (2D) 207 Pb– 1 H heteronuclear correlation (HETCOR) NMR spectra can be acquired in less than half an hour from only ca. 4 μL of perovskite material. Modest relayed DNP enhancements on the order of 1 to 20 were obtained for perovskites. The cryogenic temperatures (110 K) used for DNP experiments also provide a significant boost in sensitivity. Consequently, it was possible to obtain the 207 Pb solid-state NMR spectrum of a 300 nm thick model thin film of CH 3 NH 3 PbI 3 in 34 h by performing solid-state NMR experiments with a sample temperature of 110 K. This result demonstrates the possibility of using NMR spectroscopy for characterization of perovskite thin films.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Quantitative Prediction of Optical Absorption in Molecular Solids from an Optimally Tuned Screened Range-Separated Hybrid Functional

In this work, we show that fundamental gaps and optical spectra of molecular solids can be predicted quantitatively and nonempirically within the framework of time-dependent density functional theory (TDDFT) using the recently developed optimally tuned screened range-separated hybrid (OT-SRSH) functional approach. In this scheme, the electronic structure of the gas-phase molecule is determined by optimal tuning of the range-separation parameter in a range-separated hybrid functional. Screening and polarization in the solid state are taken into account by adding long-range dielectric screening to the functional form, with the modified functional used to perform self-consistent periodic-boundary calculations for the crystalline solid. We provide a comprehensive benchmark for the accuracy of our approach by considering the X23 set of molecular solids and comparing results obtained from TDDFT with those obtained from many-body perturbation theory in the GW-BSE approximation. We additionally compare results obtained from dielectric screening computed within the random-phase approximation to those obtained from the computationally more efficient many-body dispersion approach and find that this influences the fundamental gap but has little effect on the optical spectra. Our approach is therefore robust and can be used for studies of molecular solids that are typically beyond the reach of computationally more intensive methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Materials Characterization by Dynamic Nuclear Polarization-Enhanced Solid-State NMR Spectroscopy

Here, high-resolution solid-state NMR spectroscopy is a powerful tool for the study of organic and inorganic materials because it can directly probe the symmetry and structure at nuclear sites, the connectivity/bonding of atoms and precisely measure interatomic distances. However, NMR spectroscopy is hampered by intrinsically poor sensitivity; consequently, the application of NMR spectroscopy to many solid materials is often infeasible. High-field dynamic nuclear polarization (DNP) has emerged as a technique to routinely enhance the sensitivity of solid-state NMR experiments by 1–3 orders of magnitude. This Perspective gives a general overview of how DNP-enhanced solid-state NMR spectroscopy can be applied to a variety of inorganic and organic materials. DNP-enhanced solid-state NMR experiments provide unique insights into the molecular structure, which makes it possible to form structure–activity relationships that ultimately assist in the rational design and improvement of materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Model for the Solid–Liquid Interfacial Free Energy at High Pressures

The free energy involved in the formation of an interface between two phases (e.g., a solid–liquid interface) is referred to as the interfacial free energy. For the case of solidification, the interfacial free energy dictates the height of the energy barrier required to nucleate stable clusters of the newly forming solid phase and is essential for producing an accurate solidification kinetics model using classical nucleation theory (CNT)-based methods. While various methods have been proposed for modeling the interfacial free energy for solid–liquid interfaces in prior literature, many of these formulations involve making restrictive assumptions or approximations, such as the system being at or near equilibrium (i.e., the system temperature is approximately equal to the melt temperature) or that the system is at pressures close to atmospheric. However, these approximations and assumptions may break down in highly non-equilibrium situations, such as in dynamic-compression experiments where metastable liquids that are undercooled by hundreds of kelvin or over-pressurized by several gigapascals or more are formed before eventually solidifying. We derive a solid–liquid interfacial free-energy model for such high-pressure conditions by considering the enthalpies of interactions between pairs of atoms or molecules. We also consider the contribution of interface roughness (disordering) by incorporating a multilayer interface model known as the Temkin n-layer model. Our formulation is applicable to a diverse variety of materials, and we demonstrate it by developing models specifically for two different materials: water and gallium. We apply our interfacial free-energy formulation to CNT-based kinetics simulations of several suites of dynamic-compression experiments that cause liquid water to solidify to the high-pressure solid polymorph ice VII and have found good agreement to the observed kinetics with only minor empirical fitting.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Two-Dimensional Mechanics of Atomically Thin Solids on Water

Movement of a three-dimensional solid at an air–water interface is strongly influenced by the extrinsic interactions between the solid and the water. The finite thickness and volume of a moving solid causes capillary interactions and water-induced drag. In this Letter, we report the fabrication and dynamical imaging of freely floating MoS 2 solids on water, which minimizes such extrinsic effects. For this, we delaminate a synthesized wafer-scale monolayer MoS 2 onto a water surface, which shows negligible height difference across water and MoS 2 . Subsequently patterning by a laser generates arbitrarily shaped MoS 2 with negligible in-plane strain. We introduce photoswitchable surfactants to exert a lateral force to floating MoS 2 with a spatiotemporal control. Using this platform, we demonstrate a variety of two-dimensional mechanical systems that show reversible shape changes. Our experiment provides a versatile approach for designing and controlling a large array of atomically thin solids on water for intrinsically two-dimensional dynamics and mechanics.

2D materials↗
DOE OSTI2013

Nitridation Temperature Effects on Electronic and Chemical Properties of (Ga 1-x Zn x )(N 1-x O x ) Solid Solution Nanocrystals

Solid solution nanocrystals of gallium nitride–zinc oxide have been realized as potential photocatalysts for visible light driven overall water splitting. The band gap of these materials has been found to narrow further into the visible region as a function of increasing zinc oxide concentration, and thus, it is desirable to synthesize zinc oxide-rich gallium nitride–zinc oxide solid solutions. In this paper, we discuss the effects of using nitridation temperature to control zinc oxide content on the electronic and chemical properties of gallium nitride–zinc oxide solid solution nanostructures. The effect of nitridation temperature was studied using X-ray absorption fine structure (XAFS), including both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), and X-ray excited optical luminescence (XEOL). It was determined that using nitridation temperature as a method of controlling zinc oxide concentration results in solid solutions with poor crystallinity, phase separation, and mixed surface oxide formation. These findings suggest that many complications arise from using nitridation temperature to control zinc oxide concentration in gallium nitride–zinc oxide solid solutions, and thus, it is possible that the resultant materials would exhibit poor photocatalytic activity.

Ward, Matthew James↗
DOE OSTI2014

Microwave spectroscopic observation of distinct electron solid phases in wide quantum wells

In high magnetic fields, two-dimensional electron systems can form a number of phases in which interelectron repulsion plays the central role, since the kinetic energy is frozen out by Landau quantization. These phases include the well-known liquids of the fractional quantum Hall effect, as well as solid phases with broken spatial symmetry and crystalline order. Solids can occur at the low Landau-filling termination of the fractional quantum Hall effect series but also within integer quantum Hall effects. Here we present microwave spectroscopy studies of wide quantum wells that clearly reveal two distinct solid phases, hidden within what in d.c. transport would be the zero diagonal conductivity of an integer quantum-Hall-effect state. Explanation of these solids is not possible with the simple picture of a Wigner solid of ordinary (quasi) electrons or holes.

42 ENGINEERING↗
DOE OSTI2015

Microwave spectroscopy of the low-filling-factor bilayer electron solid in a wide quantum well

At the low Landau filling factor termination of the fractional quantum Hall effect series, two-dimensional electron systems exhibit an insulating phase that is understood as a form of pinned Wigner solid. Here we use microwave spectroscopy to probe the transition to the insulator for a wide quantum well sample that can support single-layer or bilayer states depending on its overall carrier density. We find that the insulator exhibits a resonance which is characteristic of a bilayer solid. The resonance also reveals a pair of transitions within the solid, which are not accessible to dc transport measurements. As density is biased deeper into the bilayer solid regime, the resonance grows in specific intensity, and the transitions within the insulator disappear. These behaviours are suggestive of a picture of the insulating phase as an emulsion of liquid and solid components.

Science & Technology - Other Topics↗
DOE OSTI2014

Solids between the mechanical extremes of order and disorder

For over a century, physicists have described real solids in terms of perturbations about perfect crystalline order. Such an approach takes us only so far: a glass, another ubiquitous form of rigid matter, cannot be described in any meaningful sense as a defected crystal. Is there an opposite extreme to a crystal—a solid with complete disorder—that forms an alternative starting point for understanding real materials? Here, we argue that the solid comprising particles with finite-ranged interactions at the jamming transition constitutes such a limit. It has been shown that the physics associated with this transition can be extended to interactions that are long ranged. We demonstrate that jamming physics is not restricted to amorphous systems, but dominates the behaviour of solids with surprisingly high order. Just as the free-electron and tight-binding models represent two idealized cases from which to understand electronic structure, we identify two extreme limits of mechanical behaviour. Thus, the physics of jamming can be set side by side with the physics of crystals to provide an organizing structure for understanding the mechanical properties of solids over the entire spectrum of disorder.

Order↗
DOE OSTI2020

Insights into interfacial effect and local lithium-ion transport in polycrystalline cathodes of solid-state batteries

Interfacial issues commonly exist in solid-state batteries, and the microstructural complexity combines with the chemical heterogeneity to govern the local interfacial chemistry. The conventional wisdom suggests that “point-to-point” ion diffusion at the interface determines the ion transport kinetics. Here, we show that solid-solid ion transport kinetics are not only impacted by the physical interfacial contact but are also closely associated with the interior local environments within polycrystalline particles. In spite of the initial discrete interfacial contact, solid-state batteries may still display homogeneous lithium-ion transportation owing to the chemical potential force to achieve an ionic-electronic equilibrium. Nevertheless, once the interior local environment within secondary particle is disrupted upon cycling, it triggers charge distribution from homogeneity to heterogeneity and leads to fast capacity fading. Our work highlights the importance of interior local environment within polycrystalline particles for electrochemical reactions in solid-state batteries and provides crucial insights into underlying mechanism in interfacial transport.

25 ENERGY STORAGE↗
DOE OSTI2022

Creating two-dimensional solid helium via diamond lattice confinement

The universe abounds with solid helium in polymorphic forms. Therefore, exploring the allotropes of helium remains vital to our understanding of nature. However, it is challenging to produce, observe and utilize solid helium on the earth because high-pressure techniques are required to solidify helium. Here we report the discovery of room-temperature two-dimensional solid helium through the diamond lattice confinement effect. Controllable ion implantation enables the self-assembly of monolayer helium atoms between {100} diamond lattice planes. Using state-of-the-art integrated differential phase contrast microscopy, we decipher the buckled tetragonal arrangement of solid helium monolayers with an anisotropic nature compressed by the robust diamond lattice. These distinctive helium monolayers, in turn, produce substantial compressive strains to the surrounded diamond lattice, resulting in a large-scale bandgap narrowing up to ~2.2 electron volts. This approach opens up new avenues for steerable manipulation of solid helium for achieving intrinsic strain doping with profound applications.

42 ENGINEERING↗
DOE OSTI2020

Machine-learning informed prediction of high-entropy solid solution formation: Beyond the Hume-Rothery rules

The empirical rules for the prediction of solid solution formation proposed so far in the literature usually have very compromised predictability. Some rules with seemingly good predictability were, however, tested using small data sets. Based on an unprecedented large dataset containing 1252 multicomponent alloys, machine-learning methods showed that the formation of solid solutions can be very accurately predicted (93%). The machine-learning results help identify the most important features, such as molar volume, bulk modulus, and melting temperature. As such a new thermodynamics-based rule was developed to predict solid–solution alloys. The new rule is nonetheless slightly less accurate (73%) but has roots in the physical nature of the problem. The new rule is employed to predict solid solutions existing in the three blocks, each of which consists of 9 elements. The predictions encompass face-centered cubic (FCC), body-centered cubic (BCC), and hexagonal closest packed (HCP) structures in a high throughput manner. The validity of the prediction is further confirmed by CALculations of PHAse Diagram (CALPHAD) calculations with high consistency (94%). Since the new thermodynamics-based rule employs only elemental properties, applicability in screening for solid solution high-entropy alloys is straightforward and efficient.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Robotic four-dimensional pixel assembly of van der Waals solids

Van der Waals (vdW) solids can be engineered with atomically precise vertical composition through the assembly of layered two-dimensional materials. However, the artisanal assembly of structures from micromechanically exfoliated flakes is not compatible with scalable and rapid manufacturing. Further engineering of vdW solids requires precisely designed and controlled composition over all three spatial dimensions and interlayer rotation. Here, we report a robotic four-dimensional pixel assembly method for manufacturing vdW solids with unprecedented speed, deliberate design, large area and angle control. We used the robotic assembly of prepatterned 'pixels' made from atomically thin two-dimensional components. Wafer-scale two-dimensional material films were grown, patterned through a clean, contact-free process and assembled using engineered adhesive stamps actuated by a high-vacuum robot. We fabricated vdW solids with up to 80 individual layers, consisting of 100 x 100 μm 2 areas with predesigned patterned shapes, laterally/vertically programmed composition and controlled interlayer angle. This enabled efficient optical spectroscopic assays of the vdW solids, revealing new excitonic and absorbance layer dependencies in MoS 2 . Furthermore, we fabricated twisted $N$-layer assemblies, where we observed atomic reconstruction of twisted four-layer WS 2 at high interlayer twist angles of >= 4°. In conclusion, our method enables the rapid manufacturing of atomically resolved quantum materials, which could help realize the full potential of vdW heterostructures as a platform for novel physics and advanced electronic technologies.

42 ENGINEERING↗
DOE OSTI2015

Using “Tender” x-ray ambient pressure x-Ray photoelectron spectroscopy as a direct probe of solid-liquid interface

We report a new method to probe the solid-liquid interface through the use of a thin liquid layer on a solid surface. An ambient pressure XPS (AP-XPS) endstation that is capable of detecting high kinetic energy photoelectrons (7 keV) at a pressure up to 110 Torr has been constructed and commissioned. Additionally, we have deployed a “dip & pull” method to create a stable nanometers-thick aqueous electrolyte on platinum working electrode surface. Combining the newly constructed AP-XPS system, “dip & pull” approach, with a “tender” X-ray synchrotron source (2 keV–7 keV), we are able to access the interface between liquid and solid dense phases with photoelectrons and directly probe important phenomena occurring at the narrow solid-liquid interface region in an electrochemical system. Using this approach, we have performed electrochemical oxidation of the Pt electrode at an oxygen evolution reaction (OER) potential. Under this potential, we observe the formation of both Pt²⁺ and Pt⁴⁺ interfacial species on the Pt working electrode in situ . We believe this thin-film approach and the use of “tender” AP-XPS highlighted in this study is an innovative new approach to probe this key solid-liquid interface region of electrochemistry.

25 ENERGY STORAGE↗
DOE OSTI2017

Modeling of internal mechanical failure of all-solid-state batteries during electrochemical cycling, and implications for battery design

This study is the first quantitative analysis of mechanical reliability of all-solid state batteries. Mechanical degradation of the solid electrolyte (SE) is caused by intercalation-induced expansion of the electrode particles, within the constrains of a dense microstructure. A coupled electro-chemo-mechanical model was implemented to quantify the material properties that cause an SE to fracture. The treatment of microstructural details is essential to the understanding of stress-localization phenomena and fracture. A cohesive zone model is employed to simulate the evolution of damage. In the numerical tests, fracture is prevented when electrode-particle's expansion is lower than 7.5% (typical for most Li-intercalating compounds) and the solid-electrolyte's fracture energy higher than G c = 4 J m -2 . Perhaps counter-intuitively, the analyses show that compliant solid electrolytes (with Young's modulus in the order of E SE = 15 GPa) are more prone to micro-cracking. This result, captured by our non-linear kinematics model, contradicts the speculation that sulfide SEs are more suitable for the design of bulk-type batteries than oxide SEs. Mechanical degradation is linked to the battery power-density. Fracture in solid Li-ion conductors represents a barrier for Li transport, and accelerates the decay of rate performance.

25 ENERGY STORAGE↗
DOE OSTI2019

Ab initio investigation of the stability of electrolyte/electrode interfaces in all-solid-state Na batteries

All-solid-state batteries show great potential for achieving high energy density with less safety problems; however, (electro)chemical issues at the solid electrolyte/electrode interface may severely limit their performance. In this work, the electrochemical stability and chemical reactivity of a wide range of potential Na solid-state electrolyte chemistries were investigated using density functional theory calculations. In general, lower voltage limits are predicted for both the reduction and oxidation of Na compounds compared with those of their Li counterparts. The lower reduction limits for the Na compounds indicate their enhanced cathodic stability as well as the possibility of stable sodium metal cycling against a number of oxides and borohydrides. With increasing Na content (or chemical potential), improved cathodic stability but also reduced anodic stability are observed. An increase in the oxidation voltage is shown for Na polyanion systems, including borohydrides, NaSICON-type oxides, and aluminates, due to the covalent stabilization of the anions. In addition, the oxides exhibit remarkable chemical stability when in contact with various cathode materials (layered transition metal oxides and fluorophosphates), whereas the chalcogenides predictably display narrow electrochemical windows and high chemical reactivity. Our findings indicate some promising candidates for solid-state conductors and/or protective coating materials to enable the operation of high-energy-density all-solid-state Na batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Recent progress and future prospects of atomic layer deposition to prepare/modify solid-state electrolytes and interfaces between electrodes for next-generation lithium batteries

Lithium ion batteries (LIBs) are encouraging electrochemical devices with remarkable properties including a high energy/power density, fast charging capability, and low self-discharge rate. Further increase in energy density as well as safe usage is needed for next-generation LIBs in electric transportation vehicles. Solid-state electrolytes (SSEs) are very promising for high-performance LIBs since they enable improved safety along with increased energy density compared to flammable liquid organic electrolytes. However, utilizing SSEs with a Li metal anode is very challenging due to the possibility of undesired side reactions and the formation of an unstable solid-electrolyte interphase. Therefore, it is critical to enhance the stability of SSEs against the Li anode. One feasible approach is to form a thin and conductive interlayer between the Li anode and solid-state electrolyte. Atomic layer deposition (ALD) is a unique technique for conformal coating of complex 3D structures with finely controlled film thickness (at the atomic scale). ALD coating on the surface of SSEs can be adopted for engineering solid-electrolyte interfaces with desired attributes and improved stability. In this review paper, we have discussed recent progress in implementing the ALD technique for depositing thin layers on various SSE configurations including lithium phosphorus oxynitride (LiPON), garnets, oxides, perovskites, sulphides, Li 3 BO 3 –Li 2 CO 3 (LBCO), and sodium super ionic conductors (NASICON). We have also highlighted the major areas for future research and development in the field. We believe that this review will be very helpful for directing future research on implementing ALD for synthesizing stable and high-performance SSEs with an engineered solid-electrolyte interface for next-generation electrochemical devices (e.g., Li-ion batteries, supercapacitors, and flow batteries).

36 MATERIALS SCIENCE↗