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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 1,585 records · Page 88
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Probing Hydrogen-Bond Anharmonicity in Cocrystals with Colossal Thermal Expansion

Organic cocrystals with sizable anisotropic thermal expansion (TE) are attractive building blocks for thermally responsive soft actuators. Such materials often display intermolecular H-bonding, whose thermal strength fluctuations are frequently overlooked if displacements and/or conformational changes are visible during TE. In this work, we employed variable-temperature single-crystal synchrotron diffraction to investigate the linear expansion coefficients of two organic cocrystals, 1 and 2, which exhibit colossal thermal expansivity exceeding 140 MK –1 . Despite such pronounced TE, solid-state 2 H and 13 C NMR experiments show no evidence of fast internal reorientations or large-amplitude molecular displacement during expansion. Although nondirectional π–π stacking dominates the colossal TE, our results indicate that hydrogen bonds play a non-negligible role in the anisotropic response. Molecular dynamics simulations reveal a temperature-dependent broadening of H-bond length distributions, which arises from the increased thermal sampling of an anharmonic potential energy surface. Our data support an expansion mechanism based on cooperativity in π-π interactions, accompanied by thermal softening and fluctuation-driven stretching of directional hydrogen bonds in these molecular solids. This mechanism underscores the significance of directional interactions in organic cocrystals, which is a key factor in the design of organic thermoresponsive crystalline materials.

Hernández-Morales, Ernesto A. [Univ. Nacional Auto↗
DOE OSTI2024

Functionalization of Cathode–Electrolyte Interface with Ionic Liquids for High-Performance Quasi-Solid-State Lithium–Sulfur Batteries: A Low-Sulfur Loading Study

We introduce a quasi-solid-state electrolyte lithium-sulfur (Li–S) battery (QSSEB) based on a novel Li-argyrodite solid-state electrolyte (SSE), Super P–Sulfur cathode, and Li-anode. The cathode was prepared using a water-based carboxymethyl cellulose (CMC) solution and styrene butadiene rubber (SBR) as the binder while Li6PS5F0.5Cl0.5 SSE was synthesized using a solvent-based process, via the introduction of LiF into the argyrodite crystal structure, which enhances both the ionic conductivity and interface-stabilizing properties of the SSE. Ionic liquids (IL) were prepared using lithium bis(trifluoromethyl sulfonyl)imide (LiTFSI) as the salt, with pre-mixed pyrrolidinium bis(trifluoromethyl sulfonyl)imide (PYR) as solvent and 1,3-dioxolane (DOL) as diluent, and they were used to wet the SSE–electrode interfaces. The effect of IL dilution, the co-solvent amount, the LiTFSI concentration, the C rate at which the batteries are tested and the effect of the introduction of SSE in the cathode, were systematically studied and optimized to develop a QSSEB with higher capacity retention and cyclability. Interfacial reactions occurring at the cathode–SSE interface during cycling were also investigated using electrochemical impedance spectroscopy, cyclic voltammetry, and X-ray photoelectron spectroscopy supported by ab initio molecular dynamics simulations. This work offers a new insight into the intimate interfacial contacts between the SSE and carbon–sulfur cathodes, which are critical for improving the electrochemical performance of quasi-solid-state lithium–sulfur batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

Characterizing particle-based thermal storage performance using optical methods for use in next generation concentrating solar power plants

Concentrating Solar Power (CSP) generation is an attractive option for low-emission power generation; however, the high costs of thermal storage associated with concentrating solar create a large barrier for their use and adaptation into modern life. Lowering their operation costs, while maintaining high thermal storage and transfer performance is essential. Solid particle-based heat exchange systems can reduce CSP cost but are often less efficient. Efforts to increase their performance have led to use of binary size particle mixes. Presented is an optical-based thermal analysis technique used to measure near-wall thermal conductivity of particle beds essential in determining their heat exchanger efficiency. Modulated Photothermal Radiometry is used to make dynamic temperature measurements, allowing for the extraction of the most relevant thermal properties like thermal conductivity, specific heat, and effusivity. The system uses a modulated laser source causing a damped periodic heat flux, resulting in a frequency and thermal property dependent surface temperature, of which is measured using radiometry. Lock-In techniques are used to extrapolate the amplitude of the signal. Plotting the amplitude against the root angular frequency allows for effusivity measurement by ratio to a known sample. Using specific heat measurements from literature and density measurements, the thermal conductivity of the particle mixes can be calculated. The simplicity of MPTR to probe through the depth of the bed is ideal for use in CSP for dynamic thermal performance monitoring.

Corona, Javier↗
DOE OSTI2020

Effect of Many Modes on Self-Polarization and Photochemical Suppression in Cavities

The standard description of cavity-modified molecular reactions typically involves a single (resonant) mode, while in reality the quantum cavity supports a range of photon modes. In this work we demonstrate that as more photon modes are accounted for, physico-chemical phenomena can dramatically change, as illustrated by the cavity-induced suppression of the important and ubiquitous process of proton-coupled electron-transfer. Using a multi-trajectory Ehrenfest treatment for the photonmodes, we find that self-polarization effects become essential, and we introduce the concept of selfpolarization- modified Born-Oppenheimer surfaces as a new construct to analyze dynamics. As the number of cavity photon modes increases, the increasing deviation of these surfaces from the cavityfree Born-Oppenheimer surfaces, together with the interplay between photon emission and absorption inside the widening bands of these surfaces, leads to enhanced suppression. The present findings are general and will have implications for the description and control of cavity-driven physical processes of molecules, nanostructures and solids embedded in cavities.

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

Methyl-Driven Overhauser Dynamic Nuclear Polarization

The Overhauser effect is unique among DNP mechanisms in that it requires the modulation of the electron-nuclear hyperfine interactions. While it dominates DNP in liquids and metals, where unpaired electrons are highly mobile, Overhauser DNP is possible in insulating solids if rapid structural modulations are linked to a modulation in hyperfine coupling. In this study, we report that Overhauser DNP can be triggered by the strategic addition of a methyl group, demonstrated here in a Blatter’s radical. The rotation of the methyl group leads to a modulation of the hyperfine coupling to its protons, which in turn facilitates electron-nuclear cross-relaxation. Removal of the methyl protons, through deuteration, quenches the process, as does the reduction of the hyperfine coupling strength. This result suggests the possibility for the design of tailor-made Overhauser DNP polarizing agents for high-field MAS-DNP.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Electro-chemo-mechanical evolution of sulfide solid electrolyte/Li metal interfaces: operando analysis and ALD interlayer effects

Sulfide solid electrolytes (SE) show promise for high-performance solid-state batteries because of their high ionic conductivity and ease of processing. However, sulfide electrolytes have suffered from chemical and electrochemical instability against Li metal anodes. In this paper, we use a suite of in situ/operando microscopy and spectroscopy techniques to demonstrate that Al 2 O 3 interlayers deposited using atomic layer deposition (ALD) delay degradation at the Li/LGPS interface by modifying the solid electrolyte interphase (SEI) chemistry and morphology. Optical and scanning electron microscopy are used to rationalize the electrochemical response of the system, which is attributed to a delayed onset of mechanical degradation at the interface when ALD interlayers are used. Operando X-ray photoelectron spectroscopy demonstrates that the dynamic evolution of SEI chemistry is impacted by the presence of the ALD interlayer. In situ Auger spectroscopy and operando optical microscopy provide visual evidence of spatial heterogeneity of Li plating, which is attributed to the chemo-mechanical degradation of the ALD interphase. The implications of these observations provide valuable insights toward the development of robust interlayers for solid-state batteries.

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

Broadband THz Modulation via Solid–State Organic Electrochemical Devices

The sub-Terahertz and Terahertz bands play a critical role in next-generation wireless communication and sensing technologies, thanks to the large amount of available bandwidth in this spectral regime. While long-wavelength (microwave to mm-Wave) and short-wavelength (near-infrared to ultraviolet) devices are well-established and studied, the sub-THz to THz regime remains relatively underexplored and underutilized. Traditional approaches used in the aforementioned spectral regions are more difficult to replicate in the THz band, leading to the need for the development of novel devices and structures that can manipulate THz radiation effectively. Herein a novel organic, solid-state electrochemical device is presented, capable of achieving modulation depths of over 90% from ≈500 nm of a conducting polymer that switches conductivity over a large dynamic range upon application of an electronically controllable external bias. The stability of such devices under long-term, repeated voltage switching, as well as continuous biasing at a single voltage, is also explored. Switching stabilities and long-term bias stabilities are achieved over two days for both use cases. Additionally, both depletion mode (always “ON”) and accumulation mode (always “OFF”) operation are demonstrated. These results suggest applications of organic electrochemical THz modulators in large area and flexible implementations.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Interfacial Defect of Lithium Metal in Solid-State Batteries

All-solid-state battery with Li metal anode is a promising rechargeable battery technology with high energy density and improved safety. Currently, the application of Li metal anode is plagued by the failure at the interfaces between lithium metal and solid electrolyte (SE). However, little is known about the defects at Li–SE interfaces and their effects on Li cycling, impeding further improvement of Li metal anodes. Herein, by performing large-scale atomistic modeling of Li metal interfaces with common SEs, we discover that lithium metal forms an interfacial defect layer of nanometer-thin disordered lithium at the Li–SE interfaces. Further, this interfacial defect Li layer is highly detrimental, leading to interfacial failure such as pore formation and contact loss during Li stripping. By systematically studying and comparing incoherent, coherent, and semi-coherent Li–SE interfaces, we find that the interface with good lattice coherence has reduced Li defects at the interface and has suppressed interfacial failure during Li cycling. Our finding discovered the critical roles of atomistic lithium defects at interfaces for the interfacial failure of Li metal anode, and motivates future atomistic-level interfacial engineering for Li metal anode in solid-state batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Chemical Bond Covalency in Superionic Halide Solid‐State Electrolytes

Abstract Halide solid‐state electrolytes (SSEs) are promising superionic conductors with high oxidative stability and ionic conductivity, making them attractive for all‐solid‐state lithium‐ion batteries. However, most studies have focused on ion‐stacking structures, overlooking the role of bond characteristics in ionic transport. Here, we investigate bond dynamics and the superionic transition (SIT) in bromide electrolyte, Li 3 InBr 6 , using synchrotron X‐ray techniques and ab initio molecular dynamics (AIMD) simulations. We demonstrate that the SIT in halide SSEs is driven by a thermally induced transition in bonding character (ionic to covalent) rather than a change in crystal phase. AIMD simulations further reveal enhanced Li⁺ diffusion and collective anion motion at elevated temperatures. Expanding our study to Li 3 LnBr 6 (Ln = Gd, Tb, Ho, Tm, and Lu), we confirm the widespread occurrence of SIT in this material class, with Li 3 GdBr 6 exhibiting the highest ionic conductivity (5.2 mS cm −1 at 298 K). More importantly, the ionic‐covalent transition is highly tunable through electrolyte modifications, such as cation/anion substitution and synthesis methods. Our findings provide a new perspective on ionic transport, highlighting the critical role of chemical bond characteristics in halide SSEs.

Chemistry↗
DOE OSTI2022

Understanding Instability in Formamidinium Lead Halide Perovskites: Kinetics of Transformative Reactions at Grain and Subgrain Boundaries

Transformative and reconstructive reactions impart significant structural changes at particle boundaries of hybrid perovskites, which influence environmental stability and optoelectronic properties of these materials. Here, we investigate the moisture-induced transformative reactions in formamidinium based perovskites FAPbX 3 (X=I, Br) and show that the ambient stability of these materials can be adjusted from a few hours to several months. For FAPbI 3 , roles of water vapor, particle size, and light illumination on the kinetic pathways of the cubic (a) transformation to the hexagonal (d) phase are analyzed by X-ray diffraction, optical microscopy, photoluminescence and solid-state NMR spectroscopy techniques. The grain and sub-grain boundaries exhibit different α→δ-FAPbI 3 phase transformation kinetics. Our study suggests that the dynamic transformation involves the local water-induced dissolution of the cubic phase occurring at the crystal surfaces followed by precipitation of the hexagonal phase. Insights into structures and dynamics of a kinetically trapped α-|δ-FAPbI 3 are obtained by 1 H, 2 H, and 207 Pb ssNMR spectroscopy.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Mechanisms of Asymmetric Membrane Formation in Nonsolvent-Induced Phase Separation

We report the first simulations of nonsolvent-induced phase separation (NIPS) that predict membrane microstructures with graded asymmetric pore size distribution. In NIPS, a polymer solution film is immersed in a nonsolvent bath, enriching the film in nonsolvent, and leading to phase separation that forms a solid polymer-rich membrane matrix and polymer-poor membrane pores. We demonstrate how mass-transfer-induced spinodal decomposition, thermal fluctuations, and glass-transition dynamics implemented with mobility contrast between the polymer-rich and polymer-poor phases are essential to the formation of asymmetric membrane microstructures. Specifically, we show that the competition between the propagation of the phase-separation and glass-transition fronts determines the degree of pore-size asymmetry. In conclusion, we also explore the sensitivity of these microstructures to the initial film composition, and compare their formation in 2D and 3D.

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

Maximizing long-term biohydrogen production with Clostridium thermocellum for high solids conversion of lignocellulosic biomass

Biological hydrogen production from lignocellulosic biomass sustainably couples organic waste reduction with renewable energy generation. Efficient conversion is challenged by the structural complexity of lignocellulose and resulting recalcitrance to enzymatic degradation. Clostridium thermocellum natively breaks down biomass with highly effective hemi-/cellulases systems (i.e., cellulosomes) and generates hydrogen in anaerobic cultivation, creating a compelling platform for lignocellulosic biohydrogen production. Achieving commercially viable production rates requires balancing high biomass loading and throughput against uniform mixing conditions required for enzyme dispersion, pH and temperature control, and efficient hydrogen and metabolite removal in continuous operation. To address these barriers to process intensification, we implemented novel reactor and process designs for high-solids lignocellulosic biomass fermentations using the C. thermocellum KJC19-9 strain, genetically engineered for co-utilization of cellulose and hemicellulose sugars (i.e., xylose). Via computational fluid dynamics (CFD) modeling and experimental validation, we achieved a >50% improvement in biohydrogen production with an improved anchor-type impeller morphology, coupled to a threefold reduction in agitation rate. To further reduce rheological constraints and accumulation of toxic metabolites, we then transitioned the process to sequencing fed-batch operation. The resulting process generated 24.87 L H 2 L −1 from 160 g L −1 of deacetylated and mechanically refined (DMR)-pretreated corn stover biomass over 16 days while solubilizing >95% of influent cellulose and hemicellulose, setting a new performance benchmark for continuous production of biohydrogen from lignocellulose.

08 HYDROGEN↗
DOE OSTI2026

Revealing EDL-driven reduction mechanisms in binary, ternary, and quaternary fluorinated electrolytes via an integrated MD–DFT–ML framework

Accurately predicting solid electrolyte interphase (SEI) formation requires explicitly resolving the electric double layer (EDL) structure, which deviates significantly from that of the bulk electrolyte. Although an established molecular dynamics (MD) and Density Functional Theory (DFT) framework can model SEI formation by evaluating reduction reactions of local clusters in the EDL, it suffers from a combinatorial computational bottleneck. To overcome this limitation, we introduce a machine-learning-accelerated simulation workflow (MD–DFT–ML), integrating a gradient-boosted regression model trained on EDL composition data to efficiently predict reduction potentials. We apply this framework to seven fluorinated electrolytes comprising fluorinated anions, a fluorinated ester solvent, two types of diluent (ion-solvating ester vs. non-solvating ether), and an FEC additive. The analysis shows that the EDL selectively accumulates cation-binding species; consequently, the non–cation-binding ether diluent rarely enters the EDL and makes minimal contributions to SEI formation. DFT calculations on statistically representative EDL clusters provide reduction potentials and fluorine-release pathways, while the ML model, which substantially reduces the DFT workload, predicts cluster reduction energies with a mean absolute error of 0.1 eV. The combined MD–DFT–ML approach also quantifies contributions from different sources to LiF formation in the SEI. This methodology establishes a generalizable route for multiscale modeling electrolyte and interphase design for next-generation electrochemical energy-storage systems.

DFT-MD-ML workflow↗
DOE OSTI2022

Atomistic modeling of LiF microstructure ionic conductivity and its influence on nucleation and plating

We report the formation and degradation of the solid electrolyte interphase (SEI) and its underlying transport properties play an essential role in the overall performance of lithium-ion batteries. This paper presents classical molecular dynamics studies on polycrystalline inorganic lithium fluoride (LiF) layers to model and predict the SEI transport properties. The ionic conductivity is obtained from the lithium-ion diffusivity in polycrystalline structures of LiF using the Nernst-Einstein relation. The predicted molecular dynamics data are used in a continuum scale phase-field model to evaluate the plating kinetics under fast charging conditions. The analysis emphasizes that the SEI ionic conductivity properties impact the plating dynamics, where SEI's low ion conductivity value is prone to large plating and subsequent capacity degradation. The combination of atomic and continuum scale studies shown herein lays a foundation to tune in SEI transport properties to decrease the amount of lithium plating and improve the performance of fast-charging batteries.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2020

Liquid helium fluid dynamics studies. Final Technical Report

Future high energy physics accelerators depend on a number of advanced technologies to open the many doors of scientific discovery. Among these advanced technologies, superconducting magnets and superconducting radio frequency (SRF) cavities are the backbone of the accelerator and detector systems. But all these low temperature systems depend critically on successful and reliable operation of their supporting technologies, among which the liquid helium cooling system is of the utmost importance. To improve the quality of these systems both in terms of efficiency and reliability, a robust helium cryogenics research and development (R&D) effort is required. The proposed research to be conducted by the FSU cryogenics group aims to produce fundamental knowledge that meets this R&D need. The projects that we have completed over the past grant period at Florida State University consist of experimental research on liquid helium fluid dynamics and heat transfer problems relevant to the development of future superconducting particle physics accelerators. Liquid helium is the coolant used in all such facilities and in many of these facilities He II (the low temperature phase of liquid helium also known as superfluid helium) is preferred due to its outstanding heat transfer characteristics. The work consists of two main experimental studies that probe both fundamental as well as practical aspects of liquid helium cooling. The first is a broad and fundamental study of the heat and mass transfer processes that can occur during a sudden catastrophic loss of vacuum (SCLV) incident in a superconducting accelerator. SCLV refers to the remote but extremely critical accident scenario where atmospheric pressure air is allowed to flood into the insulating vacuum system and impinge on the liquid helium cooled surfaces in the accelerator. Safe performance and recovery from such accidents is essential to the reliable operation of superconducting accelerators. The dynamics of this process is quite complex and so our approach is to conduct a series of well-orchestrated experiments that probe the various physical phenomena that can occur during an SCLV event. The experiments are coupled with analytic and numerical analysis in an effort to develop a general understanding of the process and to assist with future accelerator design and development. The second activity is directed toward fundamental understanding of heat and mass transfer in He II, which is essential to the design of superconducting magnets and radio frequency cavities in accelerators. The work consists of flow visualization of the dynamics of He II using laser assisted techniques. Two complementary techniques are used to study the fundamentals of the turbulent state. The first technique uses neutrally buoyant solid hydrogen particles to probe the flow fields of the superfluid and normal fluid components. The other technique uses laser excited He2* molecules as tracers of the normal fluid motion within the He II. The activities also included an effort to use visualization techniques to locate transient hot spots in radio frequency superconducting cavities. Such work provides valuable information about the heat transfer process in He II and its impact on the performance of superconducting devices. The research effort at Florida State University is not directly in support of a specific high energy physics experiment or facility. Rather, the work is general and coordinated with HEP accelerator laboratories to provide valuable insight that can assist with future accelerator development.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Microfabrication of a Chamber for High-Resolution, In Situ Imaging of the Whole Root for Plant–Microbe Interactions

Fabricated ecosystems (EcoFABs) offer an innovative approach to in situ examination of microbial establishment patterns around plant roots using nondestructive, high-resolution microscopy. Previously high-resolution imaging was challenging because the roots were not constrained to a fixed distance from the objective. Here, we describe a new ‘Imaging EcoFAB’ and the use of this device to image the entire root system of growing Brachypodium distachyon at high resolutions (20×, 40×) over a 3-week period. The device is capable of investigating root–microbe interactions of multimember communities. We examined nine strains of Pseudomonas simiae with different fluorescent constructs to B. distachyon and individual cells on root hairs were visible. Succession in the rhizosphere using two different strains of P. simiae was examined, where the second addition was shown to be able to establish in the root tissue. The device was suitable for imaging with different solid media at high magnification, allowing for the imaging of fungal establishment in the rhizosphere. Overall, the Imaging EcoFAB could improve our ability to investigate the spatiotemporal dynamics of the rhizosphere, including studies of fluorescently-tagged, multimember, synthetic communities.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1977

A strategy for analysis of thermal decomposition of polymeric materials

Some analytical methods developed in flammability research are reviewed. Computerized analytical systems are used to separate, identify, and quantify components of complex mixtures of low-boiling volatiles, high-boiling volatiles, and solid residues resulting from pyrolysis, oxidative degradation, and flaming combustion processes. To demonstrate the procedure for determining a material's response to a thermal flux administered under dynamic conditions, the treatment of data is reported for samples of an aromatic polyamide fabric which were degraded under isothermal conditions of 550 C following a dynamic heating rate of 100 C/min from ambient to final temperature.

Einhorn, I. N.↗
NASA NTRS1978

Solid-liquid phase transition in argon

Starting from the Lennard-Jones interatomic potential, a modified cell theory has been used to describe the solid-liquid phase transition in argon. The cell-size variations may be evaluated by a self-consistent condition. With the inclusion of cell-size variations, the transition temperature, the solid and liquid densities, and the liquid-phase radial-distribution functions have been calculated. These ab initio results are in satisfactory agreement with molecular-dynamics calculations as well as experimental data on argon.

Tsang, T.↗