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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 271 records · Page 15

A new cyclic carbonate enables high power/ low temperature lithium-ion batteries

The modern lithium-ion battery (LIB) configuration was enabled by the "magic chemistry" between ethylene carbonate (EC) and graphitic carbon anode. Despite the constant changes of cathode chemistries with improved energy densities, EC-graphite combination remained static during the last three decades. While the interphase generated by EC protects the fragile graphitic structure, the intrinsic disadvantages of EC (high viscosity, high melting point, excessive interphase growth) lead to mediocre power density and poor performances of LIB at sub-zero temperatures, where lithium depositions form upon charging. Such performance compromises arise from the fundamental dilemma between requiring effective interphase protection and high impedance from excessive growth of interphase. In this work, we designed and synthesized a "double EC" molecule as electrolyte additive to resolve the above dilemma. Erythritol bis(carbonate) (EBC) possesses lower LUMO energy level than EC and hence tends to decompose prior to EC reduction, but its weak solvation toward Li + restricts the extent of its reduction, thus minimizing the interphase thickness and the corresponding impedances. Electrolytes containing EBC enables both the charging and discharging of ampere-size LIB pouch cells at sub-zero temperatures from 0 to -20°C, demonstrating that the key approach to improve low temperature performances lies in how to tailor interphasial chemistry rather than the bulk electrolyte composition.

25 ENERGY STORAGE↗

Spectral weight reduction of two-dimensional electron gases at oxide surfaces across the ferroelectric transition

The discovery of a two-dimensional electron gas (2DEG) at the LaAlO 3 /SrTiO 3 interface has set a new platform for all-oxide electronics which could potentially exhibit the interplay among charge, spin, orbital, superconductivity, ferromagnetism and ferroelectricity. In this work, by using angle-resolved photoemission spectroscopy and conductivity measurement, we found the reduction of 2DEGs and the changes of the conductivity nature of some ferroelectric oxides including insulating Nb-lightly-substituted KTaO 3 , BaTiO 3 (BTO) and (Ca,Zr)-doped BTO across paraelectric-ferroelectric transition. We propose that these behaviours could be due to the increase of space-charge screening potential at the 2DEG/ferroelectric regions which is a result of the realignment of ferroelectric polarisation upon light irradiation. This finding suggests an opportunity for controlling the 2DEG at a bare oxide surface (instead of interfacial system) by using both light and ferroelectricity.

36 MATERIALS SCIENCE↗

Effects of multiply charged ions on microturbulence-driven electron transport in partially magnetized plasmas

Herein, nonlinear interaction between kinetic instabilities in partially magnetized plasmas in the presence of multiply-charged ion streams is investigated using kinetic simulations. It was observed by Hara and Tsikata [Phys. Rev. E 102, 023202 (2020)] that the axial ion-ion two-stream instability (IITSI) due to singly and doubly charged ion streams, coupled with the azimuthal electron cyclotron drift instability (ECDI), enhances cross-field electron transport. In the present study, it is observed that the addition of triply charged ions (as a third ion species) contributes to damping of the excited modes, leading to a reduction in the cross-field electron transport. The net instability-driven electron transport is shown to be a function not only of the azimuthal modes, such as the ECDI, but of the multiple ion species that dictate the development of additional plasma waves. It is found that trapping of the higher ion charge states within the plasma waves results in a broadening of the ion velocity distribution functions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Interfacial Engineering Using Covalent Organic Frameworks in Polymer Composites for High‐Temperature Electrostatic Energy Storage

Abstract The use of inorganic nanofillers has been an effective method to improve high‐temperature capacitive performance of dielectric polymers, though there are unmet challenges such as undesirable organic–inorganic compatibility, and low efficiencies and energy densities. Herein, a surface functionalization strategy using covalent organic frameworks (COFs) is employed to address such challenges in realizing high‐performing polymer composites. Specifically, core–shell structured nanoparticles, where ZrO 2 nanoparticles act as the core and a COF material forms the shell, are constructed and composited with the polyetherimide (PEI) matrix. The design leverages the high electron affinity ( E A ) of the outer COF shell to create energy traps, thereby capturing free charges and limiting electrical conduction. Concurrently, the low E A and wide bandgap of the ZrO 2 core introduce energy barriers to impede charge injection and migration. This orchestrated “energy level cascade” results in a marked reduction of leakage current and energy loss. The resulting polymer composite showcases an impressive discharged energy density of 6.21 J cm −3 at an efficiency above 90%, with a maximum discharged energy density reaching 7.43 J cm −3 at 150 °C. These performance metrics position the PEI/ZrO 2 @COF polymer composite to surpass or be on par with state‐of‐the‐art high‐temperature PEI composites and other advanced polymer dielectrics.

Xie, Zongliang↗

Sequential Fe Reduction, Involving Two Different Fe + Intermediates, in the Conversion Reaction of Prussian Blue in Lithium-Ion Batteries

In this work, ex situ X-ray absorption spectroscopy and in operando 57 Fe-Mössbauer spectroscopy measurements are conducted to examine in detail the ongoing reaction mechanism of potassium Prussian blue (K-PB) within the narrow [1.6–0.005 V] voltage range, and so to determine whether this material truly undergoes a conversion reaction, as we proposed elsewhere. The generation of Fe 0 is confirmed by both techniques, finding that 40 to 58% of iron gets reduced to metallic iron at 5 mV. The elucidation of the mechanism by in situ 57 Fe-Mössbauer spectroscopy further reveals a sequential process for the reduction (lithiation) of the two different iron species initially present in Prussian blue. Both high-spin Fe 2+ –N first and low-spin Fe II –C next go through the unusual Fe 1+/I formal oxidation state during the reduction process, before forming surface Fe 0 nanoparticles (NPs) below 0.48 V. Upon charge, Fe 0 NPs preferentially oxidizes into Fe + –N. Interestingly, these surprising Fe + species play an important role in decreasing the overpotential during the charge (delithiation) process with respect to other conversion systems.

25 ENERGY STORAGE↗

Characterizing Hydrated Polymers via Dielectric Relaxation Spectroscopy: Connecting Relative Permittivity, State of Water, and Salt Transport Properties of Sulfonated Polysulfones

Sulfonated polysulfone is a promising membrane material for separation and energy generation processes that rely on membranes to control the rates of small-molecule (e.g., water and ions) transport. The interactions among water molecules, ions, and the sulfonate groups in these polymers play a key role in controlling these rates of transport, but much remains unknown about these fundamental interactions in sulfonated polymers. In this study, we used dielectric relaxation spectroscopy to characterize water molecule dynamics in sulfonated polysulfone and Nafion. We found that the charged sulfonate groups contribute to a restriction of water molecule dynamics (i.e., a reduction in the characteristic time scale of dipolar motions) in a manner that is governed by the concentration and nature (i.e., conjugate base strength) of the sulfonate group. Additionally, we develop strategies to use these data to aid in modeling ion transport in sulfonated polysulfone. These results may be useful to guide engineering strategies for polymeric membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultranano Titania: Selectively Ridding Water of Persistent Organic Pollutants

Persistent organic pollutants, including the EPA's “dirty dozen”, are difficult to remove from water supplies due to their chemical stability. Here, we report a stable oxide photocatalyst, ultranano titania (d < 2 nm) doped with iron, Fe•TiUNP, that efficiently mineralizes multiple persistent pollutants including aromatic compounds plus common troublesome, difficult-to-oxidize intermediates such as formaldehyde and acetone, netting mineralization of persistent pollutants. Efficiency stems from a direct charge-transfer pathway. The key role of iron doping is to lower the reduction potential of the photogenerated electron so that it is insufficient to reduce water, thus eliminating competition from the hydrogen evolution reaction. The reduction potential of the localized electron is similarly insufficient to reduce quinone, enabling breaking aromaticity. Specific results for degrading acetone, phenol, benzoic acid, and 1,4-benzoquinone are reported.

alcohols↗

Cold Climate Integrated Heat Pump

This paper introduces development of a residential air-source integrated heat pump for cold climates (CCIHP). The heat pump is multi-functional to meet all the home comfort demands, including space cooling, space heating, domestic water heating and energy storage. The CCIHP is an ideal solution to decarbonize northern homes via providing efficient space heating and water heating to replace natural gas. It uses a three-stage compressor and a single set of heat exchangers and valves to deliver all the functions, and thus achieve cost reduction. We developed an innovative system configuration and related controls to solve typical charge unbalance in heat pumps, accelerate charge migration and smoothen mode transition in integrated heat pumps. Laboratory investigations were conducted for individual modes and verified the control functions. Laboratory tests demonstrated that the unit delivered outstanding performance. It achieved 17.0 SEER (seasonal cooling energy efficiency rating) and 11.0 HSPF (heating seasonal performance factor). In the most efficient mode (combined space cooling and water heating mode), the unit reached a total energy efficiency of 35.0 EER and required only 25 minutes to heat a 50-gallon tank of water. The CCIHP can heat 1.7 GPM water from 58 to 125°F in a direct flow-through, when the ambient temperature is above 47°F. In a dedicated water heating mode using outdoor air source, the heat pump operated down to 17°F, achieving a COP > 2.6, and heated 50-gallon water within 1 hour.

Shen, Bo↗

Residential Integrated Heat Pump to Meet All the Home Comfort Needs

This paper will introduce development and field trial of a residential air-source integrated heat pump for cold climates. The heat pump is multi-functional to meet all the home comfort demands, including space cooling, space heating, domestic water heating. The integrated heat pump is an ideal solution to decarbonize northern homes via providing efficient space heating and water heating to replace natural gas. It uses a three-stage compressor and a single set of heat exchangers and valves to deliver all the functions, and thus achieve cost reduction. We developed an innovative system configuration and related controls to solve typical charge unbalance, accelerate charge migration and smoothen mode transition in integrated heat pumps. Laboratory investigations were conducted for individual modes and verified the control functions. Laboratory tests demonstrated that the unit delivered outstanding performance. It achieved 17.0 SEER (seasonal cooling energy efficiency rating) and 11.0 HSPF (heating seasonal performance factor). In the most efficient mode (combined space cooling and water heating mode), the unit reached a total energy efficiency > 30.0 EER and required only 25 minutes to heat a 50-gallon tank of water. One heat pump prototype is going through a field trial since April, 2023 in Syracuse, New York. The one-year field test results are summarized.

Shen, Bo↗

A study of the 2H(e, e ' p)X reaction at large 4-momentum transfers and high missing momenta

The short-range region (r < 1 fm) of the nucleon-nucleon potential may be studied via deuteron electro-disintegration. Such an experiment was done at Hall C of Jefferson Lab at 4-momentum transfers of Q^2 = 4.07 (GeV/c)^2 and reaching missing momenta up to 900 MeV/c. At such settings, complications arising from Meson Exchange Currents (MEC) and Isobar Currents are expected to be signifi cantly minimized, as well as Final State Interactions (FSI) at recoiling angles of ¿_Xq ~ 40 deg. This makes comparisons of experimental and theoretical cross sections less model dependent. A luminosity study was done to determine the reduction of liquid deuterium targets with increasing beam current. A 2.8% in the charge yield was found between 0 to 70 µA. Electron scattering from the walls of the target chamber was determined to be negligible, but caution was taken by considering scattering events away from the walls. A neutron was found to be contained in the missing mass spectrum for each missing momentum setting. Extraction of the deuteron total cross section is still on going.

Love, Shawn [California State Univ. (CalState), Lo↗

Quantifying the relationship between electric field enhancement and plasmon-driven electron transfer

Plasmonic materials interact strongly with light to create localized, out-of-equilibrium environments with intense electromagnetic fields known as hotspots. After forming, hotspots dissipate energy into their surroundings and can transfer energy and charge carriers to nearby molecules, giving plasmonic materials the potential to drive reactions with sunlight. However, the field needs a better mechanistic understanding of plasmon–molecule interactions and how the local plasmon environment, specifically the electromagnetic field enhancement and spatial distribution of hotspots, impacts the reaction yield. Here, in this work, we mapped plasmon-driven charge transfer across ordered plasmonic substrates using diffraction-limited surface-enhanced Raman spectroscopy (SERS) microscopy to understand the relationship between the average local electric field enhancement and charge transfer reaction yield. We tracked the plasmon-induced electron transfer to buckminsterfullerene (C 60 ) and found that areas with the greatest SERS intensity were not the areas with the greatest ensemble-averaged reduction of C 60 , suggesting that areas with higher electric field enhancement—or “hotter,” more enhancing hotspots—do not improve the charge transfer reaction yield. This work shows that efforts to improve plasmon-driven charge transfer should not merely focus on creating substrates with extremely enhancing regions but also consider how other factors could optimize photoreduction yields.

Koble, MaKenna M. [Univ. of Minnesota, Minneapolis↗

Heavy-Duty Nonroad Material Handler Electrification Part 2: Energy Efficiency and Performance Evaluation

Decarbonization efforts achieved through electrification in nonroad mobile machinery can realize a reduction in fuel consumption of more than 20%, thanks to concepts familiar to light-duty passenger vehicles. This case study compares the results of a hybrid-electric material handler to its conventional counterpart, utilizing machine-specific drive cycles presented in part one of this paper series. The hybrid prototype features an extended-range electric vehicle (EREV) powertrain that demonstrated substantial energy efficiency improvements. Specifically, there was a reduction in equivalent fuel consumption of 75% when operating in electric-only mode, and 33% when maintaining the battery by charging with an on-board generator. Together, the efficiency improvements can be extrapolated over a low-intensity, 8-h shift characterized by significant idle time and highly dynamic engine load for a 47% reduction in net energy consumption. Key technologies that led to this improvement included engine downsizing and decoupling, regenerative braking, and an electrohydraulic pump unit with advanced controls. Finally, his study explains details of the powertrain architecture and subsystems that were implemented on a demonstration vehicle, control strategies used to meet project goals, and an analysis of energy consumption from testing on a closed course. Also included in this study is a discourse on comparison metrics that can be used for quantifying the energy consumption differences between hybrid-electric and conventional diesel powertrains in nonroad mobile machinery.

25 ENERGY STORAGE↗

Discovery and characterization of an acridine radical photoreductant

Not provided.Photoinduced electron transfer (PET) is a phenomenon whereby the absorption of light by a chemical species provides an energetic driving force for an electron-transfer reaction. This mechanism is relevant in many areas of chemistry, including the study of natural and artificial photosynthesis, photovoltaics and photosensitive materials. In recent years, research in the area of photoredox catalysis has enabled the use of PET for the catalytic generation of both neutral and charged organic free-radical species. These technologies have enabled previously inaccessible chemical transformations and have been widely used in both academic and industrial settings. Such reactions are often catalysed by visible-light-absorbing organic molecules or transition-metal complexes of ruthenium, iridium, chromium or copper. Although various closed-shell organic molecules have been shown to behave as competent electron-transfer catalysts in photoredox reactions, there are only limited reports of PET reactions involving neutral organic radicals as excited-state donors or acceptors. This is unsurprising because the lifetimes of doublet excited states of neutral organic radicals are typically several orders of magnitude shorter than the singlet lifetimes of known transition-metal photoredox catalysts. Here we document the discovery, characterization and reactivity of a neutral acridine radical with a maximum excited-state oxidation potential of -3.36 volts versus a saturated calomel electrode, which is similarly reducing to elemental lithium, making this radical one of the most potent chemical reductants reported. Spectroscopic, computational and chemical studies indicate that the formation of a twisted intramolecular charge-transfer species enables the population of higher-energy doublet excited states, leading to the observed potent photoreducing behaviour. Finally, we demonstrate that this catalytically generated PET catalyst facilitates several chemical reactions that typically require alkali metal reductants and can be used in other organic transformations that require dissolving metal reductants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Intrinsic Kinetic Limitations in Substituted Lithium-Layered Transition-Metal Oxide Electrodes

Substituted Li-layered transition-metal oxide (LTMO) electrodes such as Li x Ni y Mn z Co 1-y-z O 2 (NMC) and Li x Ni y Co 1-y-z Al z O 2 (NCA) show reduced first cycle Coulombic efficiency (90-87% under standard cycling conditions) in comparison with the archetypal Li x CoO 2 (LCO; similar to 98% efficiency). Focusing on Li x Ni 0.8 Co 0.15 Al 0.0.5 O 2 as a model compound, we use operando synchrotron X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) spectroscopy to demonstrate that the apparent first-cycle capacity loss is a kinetic effect linked to limited Li mobility at x > 0.88, with near full capacity recovered during a potentiostatic hold following the galvanostatic charge- discharge cycle. This kinetic capacity loss, unlike many capacity losses in LTMOs, is independent of the cutoff voltage during delithiation and it is a reversible process. The kinetic limitation manifests not only as the kinetic capacity loss during discharge but as a subtle bimodal compositional distribution early in charge and, also, a dramatic increase of the charge-discharge voltage hysteresis at x > 0.88. 7 Li NMR measurements indicate that the kinetic limitation reflects limited Li transport at x > 0.86. Electrochemical measurements on a wider range of LTMOs including Li x (Ni,Fe) y Co 1-y O 2 suggest that 5% substitution is sufficient to induce the kinetic limitation and that the effect is not limited to Ni substitution. In this paper, we outline how, in addition to a reduction in the number of Li vacancies and shrinkage of the Li-layer size, the intrinsic charge storage mechanism (two-phase vs solid-solution) and localization of charge give rise to additional kinetic barriers in NCA and nonmetallic LTMOs in general.

25 ENERGY STORAGE↗

Trap Passivation for Reducing On-Resistance and Saturation Voltage in Wafer-Bonded InGaAs-Channel/GaN-Drain Vertical FETs

High frequency and high power are the driving forces behind semiconductor transistor technology. However, conventional devices have the tradeoff of either being high speed or high breakdown—but not both. Wafer-bonded current aperture vertical electron transistors (BAVETs) help eliminate the tradeoff by combining a high-speed III-As channel to a high-breakdown III-N drift region. The device presented herein comprises of an InAlAs gate-barrier/InGaAs channel, wafer-bonded to an InGaN/GaN drift region, with the InGaAs/InGaN interface referred to as the wafer-bonded interface (WBI). The electronic behavior of WBIs is yet less known but necessary in realizing the potential of a BAVET. Herein, strong trap activity at the WBI is shown to be the cause of abnormally high saturation voltage ( V DS_SAT ) in BAVETs. The traps cause unintentional space charge (SC) region in the drain region of the device. This causes a drain resistance, a higher ON-resistance ( R ON ), and a higher V DS_SAT . Here, the challenge is overcome by hydrogen passivation of traps at WBI by using a p-doping for the InAlAs layer, which reduces the trap-charge concentration at the WBI. Consequently, the width of the SC region is reduced and a reduction in V DS_SAT is demonstrated, wherein it reduces from >12 to 5 V.

36 MATERIALS SCIENCE↗

Fluorinated Rocksalt Cathode with Ultra‐high Active Li Content for Lithium‐ion Batteries

Abstract The key to increasing the energy density of lithium‐ion batteries is to incorporate high contents of extractable Li into the cathode. Unfortunately, this triggers formidable challenges including structural instability and irreversible chemistry under operation. Here, we report a new kind of ultra‐high Li compound: Li 4+ x MoO 5 F x (1≤ x ≤3) for cathode with an unprecedented level of electrochemically active Li (>3 Li + per formula), delivering a reversible capacity up to 438 mAh g −1 . Unlike other reported Li‐rich cathodes, Li 4+ x MoO 5 F x presents distinguished structure stability to immunize against irreversible behaviors. Through spectroscopic and electrochemical techniques, we find an anionic redox‐dominated charge compensation with negligible oxygen release and voltage decay. Our theoretical analysis reveals a “reductive effect” of high‐level fluorination stabilizes the anionic redox by reducing the oxygen ions in pure‐Li conditions, enabling a facile, reversible, and high Li‐portion cycling.

Pei, Yi↗

Fluorinated Rocksalt Cathode with Ultra-high Active Li Content for Lithium-ion Batteries

The key to increasing the energy density of lithium-ion batteries is to incorporate high contents of extractable Li into the cathode. Unfortunately, this triggers formidable challenges including structural instability and irreversible chemistry under operation. Here, we report a new kind of ultra-high Li compound: Li 4+x MoO 5 F x (1≤x≤3) for cathode with an unprecedented level of electrochemically active Li (>3 Li + per formula), delivering a reversible capacity up to 438 mAh g –1 . Unlike other reported Li-rich cathodes, Li 4+x MoO 5 F x presents distinguished structure stability to immunize against irreversible behaviors. In this work, through spectroscopic and electrochemical techniques, we find an anionic redox-dominated charge compensation with negligible oxygen release and voltage decay. Our theoretical analysis reveals a “reductive effect” of high-level fluorination stabilizes the anionic redox by reducing the oxygen ions in pure-Li conditions, enabling a facile, reversible, and high Li-portion cycling.

36 MATERIALS SCIENCE↗

Single electron–hole pair sensitive silicon detector with surface event discrimination

Here, we demonstrate single electron-hole pair resolution in a single-sided, contact-free 1 cm$^2$ by 1 mm thick Si crystal operated at 48 mK, with a baseline energy resolution of 3 eV. This crystal can be operated at voltages in excess of $\pm50$ V, resulting in a measured charge resolution of 0.06 electron-hole pairs. The high aluminum coverage ($\sim$70%) of this device allows for the discrimination of surface events and separation of events occurring near the center of the detector from those near the edge. We use this discrimination ability to show that dark events seen in previous detectors of a similar design are likely dominated by charge leakage along the side wall of the device. We saw only a small reduction in dark event rate with this biasing scheme, further suggesting that sidewall and edge-dominated processes are responsible for the majority of these events.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗