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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 1,171 records · Page 65
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Spatially Distributed Ramp Reversal Memory in VO 2

Ramp‐reversal memory has recently been discovered in several insulator‐to‐metal transition materials where a non‐volatile resistance change can be set by repeatedly driving the material partway through the transition. This study uses optical microscopy to track the location and internal structure of accumulated memory as a thin film of VO 2 is temperature cycled through multiple training subloops. These measurements reveal that the gain of insulator phase fraction between consecutive subloops occurs primarily through front propagation at the insulator‐metal boundaries. By analyzing transition temperature maps, it is found, surprisingly, that the memory is also stored deep inside both insulating and metallic clusters throughout the entire sample, making the metal‐insulator coexistence landscape more rugged. This non‐volatile memory is reset after heating the sample to higher temperatures, as expected. Diffusion of point defects is proposed to account for the observed memory writing and subsequent erasing over the entire sample surface. By spatially mapping the location and character of non‐volatile memory encoding in VO 2 , this study results enable the targeting of specific local regions in the film where the full insulator‐to‐metal resistivity change can be harnessed in order to maximize the working range of memory elements for conventional and neuromorphic computing applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Direct Observation of Defect‐Aided Structural Evolution in a Nickel‐Rich Layered Cathode

Abstract Ni‐rich LiNi 1− x − y Mn x Co y O 2 (NMC) layered compounds are the dominant cathode for lithium ion batteries. The role of crystallographic defects on structure evolution and performance degradation during electrochemical cycling is not yet fully understood. Here, we investigated the structural evolution of a Ni‐rich NMC cathode in a solid‐state cell by in situ transmission electron microscopy. Antiphase boundary (APB) and twin boundary (TB) separating layered phases played an important role on phase change. Upon Li depletion, the APB extended across the layered structure, while Li/transition metal (TM) ion mixing in the layered phases was detected to induce the rock‐salt phase formation along the coherent TB. According to DFT calculations, Li/TM mixing and phase transition were aided by the low diffusion barriers of TM ions at planar defects. This work reveals the dynamical scenario of secondary phase evolution, helping unveil the origin of performance fading in Ni‐rich NMC.

Li, Shuang↗
DOE OSTI2020

Direct observation of defect-aided structural evolution in Ni-rich layered cathode

Ni-rich LiNi 1-x-y Mn x Co y O 2 (NMC) layered compounds have become the dominated cathode for lithium ion batteries. The role of crystallographic defects on their structure evolution and consequent performance degradation during electrochemical cycling is not yet fully understood. In this work, we investigated the structural evolution of Ni-rich NMC cathode in a solid-state cell via in-situ transmission electron microscopy. We identified antiphase boundary (APB) and twin boundary (TB) separating layered phases played an important role on phase change. Upon the lithium depletion, the APB extends across the layered structure, while Li/transition metal (TM) ion mixing in the layered phases is detected to induce the rock-salt phase formation along the coherent TB. According to DFT calculations, Li/TM mixing and phase transition are aided by the low diffusion barriers of TM ions at planar defects. Finally, this work reveals the dynamical scenario of secondary phase evolution, which helps to unveil the origin of performance fading in Ni-rich NMC.

25 ENERGY STORAGE↗
DOE OSTI2023

Multiscale simulations reveal TDP-43 molecular-level interactions driving condensation

The RNA-binding protein TDP-43 is associated with mRNA processing and transport from the nucleus to the cytoplasm. TDP-43 localizes in the nucleus as well as accumulating in cytoplasmic condensates such as stress granules. Aggregation and formation of amyloid-like fibrils of cytoplasmic TDP-43 are hallmarks of numerous neurodegenerative diseases, most strikingly present in >90% of amyotrophic lateral sclerosis (ALS) patients. If excessive accumulation of cytoplasmic TDP-43 causes, or is caused by, neurodegeneration is presently not known. In this work, we use molecular dynamics simulations at multiple resolutions to explore TDP-43 self- and cross-interaction dynamics. A full-length molecular model of TDP-43, all 414 amino acids, was constructed from select structures of the protein functional domains (N-terminal domain, and two RNA recognition motifs, RRM1 and RRM2) and modeling of disordered connecting loops and the low complexity glycine-rich C-terminus domain. All-atom CHARMM36m simulations of single TDP-43 proteins served as guides to construct a coarse-grained Martini 3 model of TDP-43. The Martini model and a coarser implicit solvent Cα model, optimized for disordered proteins, were subsequently used to probe TDP-43 interactions; self-interactions from single-chain full-length TDP-43 simulations, cross-interactions from simulations with two proteins and simulations with assemblies of dozens to hundreds of proteins. Our findings illustrate the utility of different modeling scales for accessing TDP-43 molecular-level interactions and suggest that TDP-43 has numerous interaction preferences or patterns, exhibiting an overall strong, but dynamic, association and driving the formation of biomolecular condensates.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Stable salt hydrate-based thermal energy storage materials

Heating and cooling systems in building infrastructure utilize conventional materials that account for a considerable amount of energy usage and waste. Phase change material (PCM) is considered a promising candidate for thermal energy storage that can improve energy efficiency in building systems. In this work, a novel salt hydrate-based PCM composite with high energy storage capacity, relatively higher thermal conductivity, and excellent thermal cycling stability was designed and developed. The thermal cycling stability of the PCM composite was enhanced by using dextran sulfate sodium (DSS) salt as a polyelectrolyte additive, which significantly reduced the phase segregation of salt hydrate. The energy storage capacity and the thermal conductivity of the composite were enhanced by the addition of various graphitic materials along with Borax nucleator. A significant increase in thermal cycling stability was observed for the DSS-modified composite, with over 100 thermal cycles without degradation. The final PCM composite exhibited as much as 290% increase in energy storage capacity relative to the pure salt hydrate, and approximately 20% increase in thermal conductivity. In addition, the PCM composite developed can be produced at larger scale, and can potentially change the future of heating/cooling system in building infrastructure.

42 ENGINEERING↗
DOE OSTI2021

High-performance multiblock PEMs containing a highly acidic fluorinated-hydrophilic domain for water electrolysis

The present paper describes the design and evaluation of novel hydrophilic–hydrophobic poly(arylene ether sulfone) (PAES) multiblock copolymers for their synergistic effects upon transport properties and their potential use in proton exchange membrane water electrolysis. The multiblock copolymers are prepared via a coupling reaction between (i) a hydrophilic segment consisting of a disulfonated quinone fluorinated biphenyl group that contains fluorine moieties next to the sulfonated groups to increase the acidity, and (ii) hydrophobic segments composed of non-sulfonated biphenyl sulfone to provide dimensional stability. Two different lengths (molecular weights; 5k and 10k, where k represents 10 3 g mol -1 ) of hydrophobic segments are used to investigate the effects of the membrane properties compared with those of Nafion® and PAES random copolymer (i.e., BPSH40). Atomic force microscopy images of the BPSH40 and multiblock membranes are shown to agree closely with a mesoscale simulation, thus confirming the importance of the morphological effect upon the transport properties. Furthermore, the multiblock copolymer with a higher proportion of hydrophilic segments (10 k–5k) was shown to provide enhanced performance (3.41 A cm -2 at 1.9 V) compared to the multiblock copolymer with equal proportions of hydrophilic and hydrophobic segments (10 k–10 k) due to the greater continuity of nano-sized ionic channels.

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

Efficient and mechanically-robust organic solar cells based on vertical stratification modulation through sequential blade-coating

Mechanically durable organic solar cells (OSCs) with high efficiency are deemed as the ideal candidate for the power source of the next generation wearable electronic devices. However, the brittle nature of small molecules in most high-efficiency OSCs consisting of polymer and small molecule encourages easy formation of cracks in the photoactive film under deformation. Here, the vertical composition distribution of the active layer has been well optimized through sequential blade coating to realize highly deformable while efficient OSC. The optimized morphology exhibits distinct donor-rich and homogenous region distributed along the vertical direction in the bulk. The donor-rich region provides sufficient chain entanglements and strong interfaces beneficial for mechanical robustness of film, while homogeneously mixed region offers continuous interpenetrating network to maintain high device through-put, resulting in superior efficiency of 14.4% with high crack-onset strain (COS) of 30.5%. This efficiency versus COS combination is much higher than the best combination reported in all polymer systems (COS of 15.9% and efficiency of 11.1%). To the best of our knowledge, it is the highest COS value achieved in polymer-small molecule systems. As a result, the rational control over vertical stratification demonstrated here would guide researchers in the development of innovative wearable electronics.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Revealing aggregation of non-fullerene acceptors in intermixed phase by ultraviolet-visible absorption spectroscopy

Non-fullerene acceptor (NFA) aggregation is crucial in determining bulk-heterojunction (BHJ) organic photovoltaic (OPV) performance. However, it is still a big challenge to characterize the nanostructure of NFAs in the disordered donor-acceptor intermixed phase. Here, we demonstrate a method to characterize NFA aggregation and composition in the intermixed phase by measuring NFA concentration-dependent ultraviolet-visible (UV-vis) absorption spectroscopy of BHJ films. In various polymer:NFA films, an absorption shift as a function of increasing molecular concentration (ASIMC) phenomenon is observed, and different NFA aggregation behaviors can be distinguished. The ASIMC method was then applied to study the influence of processing conditions on the NFA concentration in the intermixed phase of devices to establish a correlation with device efficiency. The current work provides a feasible tool to study the nanostructure of NFAs in the complex polymer matrix and to understand the variations in the NFA concentration in the intermixed phase under non-equilibrium conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Self-Assembly Driven Microlithography via Near-Infrared Light Activation

Current vat photopolymerization (VP) relies on UV or visible light to start the rapid crosslinking of liquid photocurable resins into 3D-printed structures. Here, we develop a self-assembly-driven photopatterning approach to photothermally generate polymeric solids by combining thermoplasmonic nanoparticles and thermoresponsive polymers, in which near-infrared (NIR) light activates thermoplasmonic heating of nanoparticles, triggering the irreversible self-assembly of thermoresponsive polymers into insoluble mesoglobules. A small amount of thermal initiator and crosslinker leads to irreversible self-assembly of polymer nanocomposites. NIR light offers deeper penetration and reduced scattering compared to UV, enabling more uniform curing of thicker or filled materials and expanded process control for composites or opaque systems. Thermoplasmonic heat generation is achieved using surface-modified gold nanorods (AuNRs) with a longitudinal localized surface plasmon resonance peak in the NIR region. Key variables such as polymer composition, molecular weight, physical interactions at the nanoparticle–polymer interface, which can be tuned by surface functionalization, AuNR concentration, and pH can be used to tailor the assembly behavior of these systems, including photothermal effect, flocculation, and cloud point temperature, and the mechanical properties of the final structures. Collectively, these results highlight a platform for photothermally-driven microlithography of polymer solids with diverse, tunable macroscopic properties, enabled by low-energy NIR light-activated self-assembly.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Melatonin-Induced Modulation of Cholesterol-Enriched Model Neuronal Membranes

Melatonin, a hormone primarily produced by the brain’s pineal gland, not only regulates circadian rhythms, but also influences the structural and biophysical properties of neuronal membranes. Its amphiphilic nature enables direct incorporation into lipid bilayers and preferential interactions with cholesterol-rich lipid rafts, critical hubs for cellular signaling and membrane organization. Despite increasing recognition of its membrane activity, the molecular basis of melatonin’s interactions with coexisting liquid-ordered (L o ) and liquid-disordered (L d ) phases remains unclear. Here, in this study, we combine small-angle neutron scattering (SANS) and all-atom molecular dynamics simulations to examine model neuronal membranes composed of DSPC, DOPC, POPC, and cholesterol. Our results show that melatonin preserves domain morphology while adopting distinct orientations within the bilayer and at the membrane interface, allowing both lateral and transmembrane bridging across lipid phases. These findings establish the molecular underpinnings of melatonin’s modulation of membrane heterogeneity and provide strong support for its receptor-independent actions.

atomistic simulations↗
DOE OSTI2025

Revisiting the Effects of Seed Liquid Water Content on Isoprene Secondary Organic Aerosol Growth

Aerosol liquid water content (LWC) has been shown to enhance partitioning of water-soluble oxygenated organic vapors into the aerosol particles and facilitate aqueous chemistry, impact SOA formation, composition, and physicochemical properties. Here, this study examines the effect of aerosol liquid water content (LWC) on isoprene SOA formation using effloresced and deliquesced ammonium sulfate ((NH 4 ) 2 SO 4 ) and sodium chloride (NaCl) seed particles in an environmental chamber with photo-oxidation extending over hours under moderate relative humidity (50%-60%). Our findings indicate that isoprene SOA mass yield is not significantly influenced (p value >> 0.05) by the phase state or the chemical identity of the seed particles within a 3–4-hour reaction time scale. Detailed molecular analysis using advanced high resolution mass spectrometry indicates that while both effloresced and deliquesced seed types produced similar molecular formula distributions, deliquesced (NH 4 ) 2 SO 4 slightly favored the production of less volatile compounds. Depth-profiling analysis by single particle mass spectrometry confirmed that isoprene SOA predominantly located on the surfaces of particles with core-shell morphologies, with partial dissolution of the effloresced inorganic salt observed even below the deliquescence relative humidity (DRH) of salt. This finding suggests that assuming dry salt core particles do not interact with SOA coatings, based on salt deliquescence points, may overlook important aqueous chemistry. These results emphasize the critical role of reaction time scale and mixing state on SOA formation and call for further research to understand LWC effects on SOA from different precursors.

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

Halogen Redox Shuttle Explains Voltage-Induced Halide Redistribution in Mixed-Halide Perovskite Devices

Voltage-induced halide segregation greatly limits the optoelectronic applications of mixed-halide perovskite devices, but a mechanistic explanation behind this phenomenon remains unclear. In this work, we use electron microscopy and elemental mapping to directly measure the halide redistribution in mixed-halide perovskite solar cells with quasi-ion-impermeable contact layers under different bias polarities to find iodide and bromide accumulation at the cathode and anode, respectively. This is consistent with a mechanism based on preferential iodide oxidation at the anode, leading to unbalanced I$^{+}_{i}$, I$^{-}_{X}$, and Br$^{-}_{X}$ fluxes. Importantly, switching the anode from "inert" Au to "active" Ag prevents segregation because Ag oxidation precludes the oxidation of lattice iodide, which suggests employing redox-active additives as a general strategy to suppress halide segregation. Finally, these results show that halide perovskite devices operate as solid-state electrochemical cells when threshold voltages are exceeded, providing fresh insight to understand the impacts of voltage bias on halide perovskite devices.

14 SOLAR ENERGY↗
DOE OSTI2023

Colloidal Clusters and Networks Formed by Oppositely Charged Nanoparticles with Varying Stiffnesses

Colloidal clusters and gels are ubiquitous in science and technology. Particle softness has a strong effect on interparticle interactions; however, our understanding of the role of this factor in the formation of colloidal clusters and gels is only beginning to evolve. Here, we report the results of experimental and simulation studies of the impact of particle softness on the assembly of clusters and networks from mixtures of oppositely charged polymer nanoparticles (NPs). Experiments were performed below or above the polymer glass transition temperature, at which the interaction potential and adhesive forces between the NPs were significantly varied. Hard NPs assembled in fractal clusters that subsequently organized in a kinetically arrested colloidal gel, while soft NPs formed dense precipitating aggregates, due to the NP deformation and the decreased interparticle distance. Importantly, interactions of hard and soft NPs led to the formation of discrete precipitating NP aggregates at a relatively low volume fraction of soft NPs. A phenomenological model was developed for interactions of oppositely charged NPs with varying softnesses. Furthermore, the experimental results were in agreement with molecular dynamics simulations based on the model. This work provides insight on interparticle interactions before, during, and after the formation of hard–hard, hard–soft, and soft–soft contacts and has impact for numerous applications of reversible colloidal gels, including their use as inks for additive manufacturing.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Hyperspectral Detection of the Fluorescence Shift between Chirality-Sorted Empty and Water-Filled Single-Wall Carbon Nanotube Enantiomers

Single-wall carbon nanotubes (SWCNTs) have extraordinary electronic and optical properties that depend strongly on their exact chiral structure and their interaction with their inner and outer environment. The fluorescence (PL) of semiconducting SWCNTs, for instance, will shift depending on the molecules with which the SWCNT’s hollow core is filled. These interaction-induced shifts are challenging to resolve on the ensemble level in samples containing a mixture of different filling contents due to the relatively large inhomogeneous line width of the ensemble SWCNT PL compared to the size of these shifts. To circumvent this inhomogeneous broadening, single-tube spectroscopy and hyperspectral imaging are often applied, which until now required time-consuming statistical studies. Here, we present hyperspectral PL microscopy combined with automated SWCNT segmenting based on either principal component analysis or a convolutional neural network, capable of both spatially and spectrally resolving the PL along the length of many individual SWCNTs at the same time and automatically fitting peak positions and line widths of individual SWCNTs. The methodology is demonstrated by accurately determining the emission shifts and line widths of thousands of left- and right-handed empty and water-filled SWCNTs coated with a chiral surfactant, resulting in four statistical distributions which cannot be resolved in ensemble spectroscopy of unsorted samples. The results demonstrate a robust method to quickly probe ensemble properties with single-enantiomer spectral resolution. Moreover, it promises to be an absolute quantitative method to characterize the relative abundances of SWCNTs with different handedness or filling content in macroscopic samples, simply by counting individual species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Strain and Defect-Tailored Magnetotransport in NiCo 2 O 4 Thin Films and Freestanding Membranes

Magnetic spinel NiCo 2 O 4 is promising for developing spintronic applications due to its high magnetic Curie temperature, high spin polarization, fast spin dynamics, and strain-tunable magnetic anisotropy, while its electronic and magnetic properties depend sensitively on epitaxial strain and disorder. Here, in this study, we use epitaxial NiCo 2 O 4 thin films and freestanding NiCo 2 O 4 membranes as model systems to reveal the complex interplay of strain and defects in determining the metallicity and magnetotransport properties of the ferrimagnetic spinel. NiCo 2 O 4 on perovskite substrates and NiCo 2 O 4 membranes exhibit insulating behaviors and spin canting, in sharp contrast to the metallic NiCo 2 O 4 films on spinel substrates that possess strong perpendicular magnetic anisotropy. Anisotropic magnetoresistance studies provide critical information about disorder-induced spin scattering and strain-induced tetragonal magnetocrystalline anisotropy, which is corroborated by comprehensive electron microscopy characterizations. Our study presents a promising venue for designing flexible magnetic memory, sensor, and spintronic applications.

36 MATERIALS SCIENCE↗