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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 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

UV-Induced Reaction Pathways in Bromoform Probed with Ultrafast Electron Diffraction

For many chemical reactions, it remains notoriously difficult to predict and experimentally determine the rates and branching ratios between different reaction channels. This is particularly the case for reactions involving short-lived intermediates, whose observation requires ultrafast methods. The UV photochemistry of bromoform (CHBr 3 ) is among the most intensely studied photoreactions. Yet, a detailed understanding of the chemical pathways leading to the production of atomic Br and molecular Br 2 fragments has proven challenging. In particular, the role of isomerization and/or roaming and their competition with direct C–Br bond scission has been a matter of continued debate. Here, in this work, gas-phase ultrafast megaelectronvolt electron diffraction (MeV-UED) is used to directly study structural dynamics in bromoform after single 267 nm photon excitation with femtosecond temporal resolution. The results show unambiguously that isomerization contributes significantly to the early stages of the UV photochemistry of bromoform. In addition to direct C–Br bond breaking within <200 fs, formation of iso-CHBr 3 (Br-CH-Br-Br) is observed on the same time scale and with an isomer lifetime of >1.1 ps. The branching ratio between direct dissociation and isomerization is determined to be 0.4 ± 0.2:0.6 ± 0.2, i.e., approximately 60% of molecules undergo isomerization within the first few hundred femtoseconds after UV excitation. The structure and time of formation of iso-CHBr 3 compare favorably with the results of an ab initio molecular dynamics simulation. The lifetime and interatomic distances of the isomer are consistent with the involvement of a roaming reaction mechanism.

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

Impact of Molecular Design on Degradation Lifetimes of Degradable Imine-Based Semiconducting Polymers

Transient electronics are a rapidly emerging field due to their potential applications in the environment and human health. Recently, a few studies have incorporated acid-labile imine bonds into polymer semiconductors to impart transience; however, understanding of the structure–degradation property relationships of these polymers is limited. In this work, we systematically design and characterize a series of fully degradable diketopyrrolopyrrole-based polymers with engineered sidechains to investigate the impact of several molecular design parameters on the degradation lifetimes of these polymers. By monitoring degradation kinetics via ultraviolet–visible spectroscopy, we reveal that polymer degradation in solution is aggregation-dependent based on the branching point and M n , with accelerated degradation rates facilitated by decreasing aggregation. Additionally, increasing the hydrophilicity of the polymers promotes water diffusion and therefore acid hydrolysis of the imine bonds along the polymer backbone. The aggregation properties and degradation lifetimes of these polymers rely heavily on solvent, with polymers in chlorobenzene taking six times as long to degrade as in chloroform. We develop a new method for quantifying the degradation of polymers in the thin film and observe that similar factors and considerations (e.g., interchain order, crystallite size, and hydrophilicity) used for designing high-performance semiconductors impact the degradation of imine-based polymer semiconductors. We found that terpolymerization serves as an attractive approach for achieving degradable semiconductors with both good charge transport and tuned degradation properties. This study provides crucial principles for the molecular design of degradable semiconducting polymers, and we anticipate that these findings will expedite progress toward transient electronics with controlled lifetimes.

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

Observation of the Interlayer Exciton Gases in WSe 2 -p:WSe 2 Heterostructures

Interlayer excitons (IXs) possess a much longer lifetime than intralayer excitons due to the spatial separation of the electrons and holes, and hence they have been pursued to create exciton condensates for decades. The recent emergence of 2D materials, such as transition-metal dichalcogenides (TMDs), and of their van der Waals heterostructures, in which two different 2D materials are layered together, has created new opportunities to study IXs. Here we present the observation of IX gases within two stacked structures consisting of hBN/WSe 2 /hBN/p:WSe 2 /hBN. The IX energies of the two different structures differed by 82 meV due to the different thicknesses of the hexagonal boron nitride spacer layer between the TMD layers. We demonstrate that the lifetime of the IXs is shortened when the temperature and the pump power increase. We attribute this nonlinear behavior to an Auger process.

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

Structural distortion and electron redistribution in dual-emitting gold nanoclusters

Deciphering the complicated excited-state process is critical for the development of luminescent materials with controllable emissions in different applications. Here we report the emergence of a photo-induced structural distortion accompanied by an electron redistribution in a series of gold nanoclusters. Such unexpected slow process of excited-state transformation results in near-infrared dual emission with extended photoluminescent lifetime. We demonstrate that this dual emission exhibits highly sensitive and ratiometric response to solvent polarity, viscosity, temperature and pressure. Thus, a versatile luminescent nano-sensor for multiple environmental parameters is developed based on this strategy. Furthermore, we fully unravel the atomic-scale structural origin of this unexpected excited-state transformation, and demonstrate control over the transition dynamics by tailoring the bi-tetrahedral core structures of gold nanoclusters. Overall, this work provides a substantial advance in the excited-state physical chemistry of luminescent nanoclusters and a general strategy for the rational design of next-generation nano-probes, sensors and switches.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

Employing Long-Range Inductive Effects to Modulate Metal-to-Ligand Charge Transfer Photoluminescence in Homoleptic Cu(I) Complexes

Four Cu(I) bis(phenanthroline) photosensitizers formulated from a new ligand structural motif (Cu1-Cu4) coded according to their 2,9-substituents, were synthesized, structurally characterized, and fully evaluated using steady-state and time-resolved absorption and photoluminescence (PL) measurements as well as electrochemistry. The 2,9-disubstituted-3,4,7,8-tetramethyl-1,10-phenanthroline ligands feature the following six-membered ring systems prepared through photochemical synthesis: 4,4-dimethylcyclohexyl (1), tetrahydro-2H-pyran-4-yl (2), tetrahydro-2H-thiopyran-4-yl (3), and 4,4-difluorocyclohexyl (4). Universally, these Cu(I) metal-to-ligand charge transfer (MLCT) chromophores display excited state lifetimes on the microseconds time scale at room temperature, including the three longest-lived homoleptic cuprous phenanthroline excited states measured to date in deaerated CH 2 Cl 2 , τ = 2.5 to 4.3 μs. This series of molecules also feature high PL quantum efficiencies (ΦPL = 5.3 to 12% in CH 2 Cl 2 ). Temperature-dependent PL lifetime experiments confirmed that all these molecules exhibit reverse intersystem crossing and display thermally activated delayed PL from a 1 MLCT excited state lying slightly above the 3 MLCT state, 1050 – 1490 cm -1 . Ultrafast and conventional transient absorption measurements confirmed that the PL originates from the MLCT excited state, which remains sterically arrested, preventing an excessive flattening distortion even when dissolved in Lewis basic CH 3 CN. Combined PL and electrochemical data provided evidence that Cu1-Cu4 are highly potent photoreductants (E ox * = -1.73 to -1.62 V vs. Fc +/o in CH 3 CN), whose potentials are altered solely based on which heteroatoms or substituents are resident on the 2,9-appended ring derivatives. It is proposed that long-range electronic inductive effects are responsible for the systematic modulation observed in the PL spectra, excited state lifetimes, as well as the ground state absorption spectra and redox potentials. Cu1-Cu4 quantitatively follow the energy gap law, correlating well with structurally related cuprous phenanthrolines and are also shown to triplet photosensitize the excited states of 9,10-diphenylanthracene with bimolecular rate constants ranging from 1.61 to 2.82 × 10 8 M –1 s –1 . Furthermore, the ability to tailor both photophysical and electrochemical properties using long-range inductive effects imposed by the 2,9-ring platforms advocates new directions for future MLCT chromophore discovery.

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

Energy and Power Evolution Over the Lifetime of a Battery

Li-ion batteries currently are dominant energy storage devices for electric vehicles. Rechargeable batteries with lower cost, longer lifetime, and higher safety are desired in support of building of a green grid infrastructure. The continued investment in new battery materials, novel battery structures, advanced manufacturing processes, and accelerated testing/validation of battery performance has led to significant progress in battery development and deployment. Battery safety/reliability, which is essential to the success of a battery technology in the real world, naturally becomes the next big topic in battery research. Recently, the increasing interest in long-duration storage, fast charging, battery secondary use, and material recycling to build a circular industry and sustainable material supply chain has compelled further attention to understand the energy/power evolution and safety over the lifetime of a battery. Here, in this short Viewpoint, we discuss some high-level analyses on the energy/power evolution of rechargeable batteries over their life cycles aiming to inspire more discussion on the safety and sustainability of some representative and emerging battery technologies.

25 ENERGY STORAGE↗
DOE OSTI2022

Phason-Dominated Thermal Transport in Fresnoite

Fast-propagating waves in the phase of incommensurate structures, called phasons, have long been argued to enhance thermal transport. Although supersonic phason velocities have been observed, the lifetimes, from which mean free paths can be determined, have not been resolved. Using inelastic neutron scattering and thermal conductivity measurements, we establish that phasons in piezoelectric fresnoite make a major contribution to thermal conductivity by propagating with higher group velocities and longer mean free paths than phonons. In this work, the phason contribution to thermal conductivity is maximum near room temperature, where it is the single largest contributing degree of freedom.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Theory-guided experimental design in battery materials research

A reliable energy storage ecosystem is imperative for a renewable energy future, and continued research is needed to develop promising rechargeable battery chemistries. To this end, better theoretical and experimental understanding of electrochemical mechanisms and structure-property relationships will allow us to accelerate the development of safer batteries with higher energy densities and longer lifetimes. This Review discusses the interplay between theory and experiment in battery materials research, enabling us to not only uncover hitherto unknown mechanisms but also rationally design more promising electrode and electrolyte materials. We examine specific case studies of theory-guided experimental design in lithium-ion, lithium-metal, sodium-metal, and all-solid-state batteries. We also offer insights into how this framework can be extended to multivalent batteries. To close the loop, we outline recent efforts in coupling machine learning with high-throughput computations and experiments. Last, recommendations for effective collaboration between theorists and experimentalists are provided.

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

Multifunctional Optical Outcouplers for Efficient and Stable White OLEDs (Final Technical Report)

Replacing fluorescence by phosphorescence in OLED-based solid-state lighting can realize the Department of Energy’s efficiency target of 83% Internal Quantum Efficiency (IQE). The principal challenge, however, is to fix the poor stability of phosphorescent blue OLEDs. To address this, we have fabricated novel plasmonic architectures that improve device stability by decreasing the exciton lifetime of the emitters without drastically decreasing the light extraction efficiency. We describe the impact on stability of these structures in high efficiency blue phosphorescent OLEDs. Although the benefit is appreciable, we find that targeting ‘bright’ triplets on phosphorescent emitter molecules is an incomplete solution, and that it is also necessary to stabilize ‘dark’ triplets formed in the host and blocking layers. We demonstrate substantial improvements in stability using the latter approach, and conclude with a discussion of potential approaches to managing dark triplets in OLEDs.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2020

The Detection of Monoclinic Zirconia and Non-Uniform 3D Crystallographic Strain in a Re-Oxidized Ni-YSZ Solid Oxide Fuel Cell Anode

The solid oxide fuel cell (SOFC) anode is often composed of nickel (Ni) and yttria-stabilized zirconia (YSZ). The yttria is added in small quantities (e.g., 8 mol %) to maintain the crystallographic structure throughout the operating temperatures (e.g., room-temperature to >800 °C). The YSZ skeleton provides a constraining structural support that inhibits degradation mechanisms such as Ni agglomeration and thermal expansion miss-match between the anode and electrolyte layers. Within this structure, the Ni is deposited in the oxide form and then reduced during start-up; however, exposure to oxygen (e.g., during gasket failure) readily re-oxidizes the Ni back to NiO, impeding electrochemical performance and introducing complex structural stresses. In this work, we correlate lab-based X-ray computed tomography using zone plate focusing optics, with X-ray synchrotron diffraction computed tomography to explore the crystal structure of a partially re-oxidized Ni/NiO-YSZ electrode. These state-of-the-art techniques expose several novel findings: non-isotropic YSZ lattice distributions; the presence of monoclinic zirconia around the oxidation boundary; and metallic strain complications in the presence of variable yttria content. This work provides evidence that the reduction–oxidation processes may destabilize the YSZ structure, producing monoclinic zirconia and microscopic YSZ strain, which has implications upon the electrode’s mechanical integrity and thus lifetime of the SOFC.

25 ENERGY STORAGE↗
DOE OSTI2020

NGC 4869 in the Coma Cluster: Twist, Wrap, Overlap, and Bend

The upgraded Giant Metrewave Radio Telescope (GMRT) has been used to image the head–tail radio galaxy NGC 4869 in the Coma cluster with an angular resolution of 6.″26 at 250–500 MHz and 2.″18 at the 1050–1450 MHz bands. The archival legacy GMRT data have also been used to image the source with angular resolutions from 4.″9 to 21.″8 at 610 MHz, 325 MHz, 240 MHz, and 150 MHz. We find that the ∼200 kpc scale radio morphology consists of five distinct regions with the clear presence of a pinch at ≈1.′4 (=38.8 kpc) and a ridge at ≈3.′4 (=94.2 kpc) from the head. The sharp bend by ∼70° at ∼3.′5 (=97 kpc) from the head is possibly due to projection effects. The radio spectra show progressive spectral steepening as a function of distance from the head and there is possibly re-acceleration of the synchrotron electrons and perhaps also magnetic field regeneration in the 6″–208″ (=2.8–96.1 kpc) region of the jet. We report a steep spectrum sheath layer enveloping a flat spectrum spine, hinting at a transverse velocity structure with a fast-moving spine surrounded by a slow-moving sheath layer. We also derive the lifetimes of the radiating electrons and equipartition parameters. A plausible explanation for the characteristic feature, a ridge of emission perpendicular to the direction of tail is the flaring of a straight, collimated radio jet as it crosses a surface brightness edge due to Kelvin–Helmholtz instabilities.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2026

Multiplet lines in seeded stimulated Mn 𝐾⁢𝛼 1 x-ray emission

We report the successful resolution of the multiplet structure of 𝐾⁢𝛼 1 x-ray emission in manganese (Mn) complexes through seeded stimulated x-ray emission spectroscopy (seeded S-XES). Using a femtosecond pump pulse above the Mn 𝐾 edge to generate simultaneous 1⁢𝑠 core holes, and a second-color tunable seed pulse to initiate the stimulated emission process, we were able to enhance individual lines within the 𝐾⁢𝛼 1 emission. This approach allows to resolve the fine multiplet features that are obscured by lifetime broadening in conventional (spontaneous) Mn 𝐾⁢𝛼 XES. The work builds on our previous observation that S-XES from Mn(II) and Mn(VII) complexes pumped at high intensities can exhibit stimulated emission without sacrificing the chemical sensitivity to oxidation states. Furthermore, this technique opens the door to controlled high-resolution electronic structure spectroscopy in transition-metal complexes beyond the core-hole lifetime, with potential applications in catalysis, inorganic chemistry, and materials science.

Chemical Physics & Physical Chemistry↗
DOE OSTI2024

Exciton polaron formation and hot-carrier relaxation in rigid Dion–Jacobson-type two-dimensional perovskites

The efficiency of two-dimensional Dion–Jacobson-type materials relies on the complex interplay between electronic and lattice dynamics; however, questions remain about the functional role of exciton–phonon interactions. Here we establish the robust polaronic nature of the excitons in these materials at room temperature by combining ultrafast spectroscopy and electronic structure calculations. We show that polaronic distortion is associated with low-frequency (30–60 cm –1 ) lead iodide octahedral lattice motions. More importantly, we discover how targeted ligand modification of this two-dimensional perovskite structure manipulates exciton–phonon coupling, exciton polaron population and carrier cooling. At high excitation density, stronger exciton–phonon coupling increases the hot-carrier lifetime, forming a hot-phonon bottleneck. Furthermore, our study provides detailed insight into the exciton–phonon coupling and its role in carrier cooling in two-dimensional perovskites relevant for developing emerging hybrid semiconductor materials with tailored properties.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Enhancing Electrochemical CO2 Conversion by Controlling Electrocatalysts' Structure

Electrochemical reduction of CO2 (CO2R) to valuable, carbon-neutral chemical feedstocks and storable fuels driven by renewable electricity has been recognized as one of the promising pathways to mitigate the greenhouse effect, reduce global demand for fossil fuels, achieve carbon neutrality, and create sustainable energy. Tremendous ongoing efforts have focused on controlling the morphology, composition, structure, size, defects, etc., of the electrocatalysts to improve product selectivity, activity, and durability to approach the feasibility of practical applications (current density higher than 200 mA/cm2 and lifetime ~1,000 hr+). This presentation will discuss how the geometry and surface composition of novel copper- and tin-based catalysts would maximize the CO2 conversion to carbon monoxide and liquid formic acid/formate in both common aqueous H-cell and electrolyzer configurations. Several spectroscopic, microscopic, and electrochemical characterization tools have been utilized to correlate the changes in the structural, physico-chemical, and electronic properties with the catalytic activity. Our work provides additional electrocatalyst design considerations for high-performance CO2 electrolysis.

Nguyen Phan, Thuy Duong↗
DOE OSTI2024

Epitaxial Core/Shell Nanocrystals of (Europium-Doped) Zirconia and Hafnia

A careful design of the nanocrystal architecture can strongly enhance the nanocrystal function. So far, this strategy has faced a synthetic bottleneck in the case of refractory oxides. Here we demonstrate the epitaxial growth of hafnia shells onto zirconia cores and pure zirconia shells onto europium-doped zirconia cores. The core/shell structures are fully crystalline. Upon shelling, the optical properties of the europium dopant are dramatically improved (featuring a more uniform coordination and a longer photoluminescence lifetime), indicating the suppression of nonradiative pathways. These results launch the stable zirconium and hafnium oxide hosts as alternatives for the established NaYF 4 systems.

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

Ultrafast photoinduced band splitting and carrier dynamics in chiral tellurium nanosheets

Trigonal tellurium (Te) is a chiral semiconductor that lacks both mirror and inversion symmetries, resulting in complex band structures with Weyl crossings and unique spin textures. Detailed time-resolved polarized reflectance spectroscopy is used to investigate its band structure and carrier dynamics. The polarized transient spectra reveal optical transitions between the uppermost spin-split H4 and H5 and the degenerate H6 valence bands (VB) and the lowest degenerate H6 conduction band (CB) as well as a higher energy transition at the Lpoint. Surprisingly, the degeneracy of the H6 CB (a proposed Weyl node) is lifted and the spin-split VB gap is reduced upon photoexcitation before relaxing to equilibrium as the carriers decay. Using ab initio density functional theory (DFT) calculations, we conclude that the dynamic band structure is caused by a photoinduced shear strain in the Te film that breaks the screw symmetry of the crystal. The band-edge anisotropy is also reflected in the hot carrier decay rate, which is a factor of two slower along the c-axis than perpendicular to it. The majority of photoexcited carriers near the band-edge are seen to recombine within 30 ps while higher lying transitions observed near 1.2 eV appear to have substantially longer lifetimes, potentially due to contributions of intervalley processes in the recombination rate. These new findings shed light on the strong correlation between photoinduced carriers and electronic structure in anisotropic crystals, which opens a potential pathway for designing novel Te-based devices that take advantage of the topological structures as well as strong spin-related properties.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Multiscale Understanding of Surface Structural Effects on High-Temperature Operational Resiliency of Layered Oxide Cathodes

The worldwide energy demand in electric vehicles and the increasing global temperature have called for development of high-energy and long-life lithium-ion batteries (LIBs) with improved high temperature operational resiliency. However, current attention has been mostly focused on cycling aging at elevated temperature, leaving considerable gaps of knowledge in the failure mechanism and practical control of abusive calendar aging and thermal runaway that are highly related to the eventual operational lifetime and safety performance of LIBs. Herein, using a combination of various in situ synchrotron X-ray and electron microscopy techniques, we report a multiscale understanding of surface structure effects involved in regulating the high temperature operational tolerance of polycrystalline Ni-rich layered cathodes. Our results collectively show that an ultraconformal poly (3,4-ethylenedioxythiophene) coating can effectively prevent LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode from undesired phase transformation and transition metal dissolution on the surface, atomic displacement and dislocations within primary particles, intergranular cracking along the grain boundaries within secondary particles, and intensive bulk oxygen release during high state-of-charge and high temperature aging. As a result, the present work highlights the essential role of surface structure controls in overcoming the multiscale degradation pathways of high-energy battery materials at extreme temperature.

25 ENERGY STORAGE↗
DOE OSTI2020

Impact of K-Optimization on Trap Concentration in (Ag,Cu)(In,Ga)Se 2 Solar Cells

Recent progress has been made in improving efficiency in Cu(In,Ga)Se 2 (CIGS) absorbers with steady increases in peak efficiency. One way this has been achieved is by adding Ag to CIGS (ACIGS) to achieve higher V OC . However, these efficiencies are still well below the Shockley-Queisser efficiency limit, and traps acting as recombination centers and compensating centers are one thing limiting the solar efficiency. Past research in CIGS has shown that alkali treatment can improve the efficiency and metastability problems in CIGS, but less is understood about the role of alkali treatments in ACIGS. Here, we investigate the impact of potassium in ACIGS through its impact on trap incorporation and minority carrier lifetime. The samples in this study were grown in a roll-to-roll coater with Mo, ACIGS, CdS, and ZnO structure. Both cells were grown identically except the second (K-optimized) cell was grown with increased K-doping of the Mo contact and was more Cu-poor near the surface to optimize the K profile. This resulted in an efficiency increase from 16.8% to 18.7% for the K-optimized cell, which was mostly due to a 65 mV V OC increase. The doping profile showed a 2X increase in acceptor concentration of the K-optimized cell (2.5×10 15 cm -3 ) which suggests that the K was better incorporated into the ACIGS after these optimizations. To characterize the traps in these cells, deep level transient and optical spectroscopy were used. The DLOS measurements showed an EV+0.98 eV trap whose concentration was reduced 10X in the K-optimized cell (4×10 14 cm -3 ). This is consistent with previous results from the alkali treatment in CIGS, which also showed a decrease in near-conduction band trap concentration [1], but the reduction was larger than previous studies possibly indicating the combination of K and Cu-poor surface may both have aided in reducing the EV+0.98 eV trap concentration. The other primary trap is the mid-gap trap (EV+0.58 eV), which was quantified using DLTS. Its concentration decreased from 9×10 13 cm -3 to 4×10 13 cm -3 in the K-optimized sample, which is a 2X reduction. Previous studies have shown this trap is likely an efficient recombination center [2], which makes sense because it is near mid-gap. This trap has also been associated with V OC instability and reduction, so reducing this trap concentration is essential to achieve high V OC and cell efficiency. To help confirm this association, time-resolved photoluminescence measurements have shown in this sample set and a previous study that the minority carrier lifetime (19 ns baseline to 56 ns K-optimized) and this EV+0.56 eV trap concentration are inversely proportional, which would be expected for a recombination-limited carrier lifetime. The K optimization of ACIGS results in significantly improved cell efficiency and reduced trap concentrations that correlate with the improved material and electrical properties. We will report on this and the impact of the K optimization on the cell metastability.

14 SOLAR ENERGY↗