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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Prescribed fires, smoke exposure, and hospital utilization among heart failure patients

Abstract Background Prescribed fires often have ecological benefits, but their environmental health risks have been infrequently studied. We investigated associations between residing near a prescribed fire, wildfire smoke exposure, and heart failure (HF) patients’ hospital utilization. Methods We used electronic health records from January 2014 to December 2016 in a North Carolina hospital-based cohort to determine HF diagnoses, primary residence, and hospital utilization. Using a cross-sectional study design, we associated the prescribed fire occurrences within 1, 2, and 5 km of the patients’ primary residence with the number of hospital visits and 7- and 30-day readmissions. To compare prescribed fire associations with those observed for wildfire smoke, we also associated zip code-level smoke density data designed to capture wildfire smoke emissions with hospital utilization amongst HF patients. Quasi-Poisson regression models were used for the number of hospital visits, while zero-inflated Poisson regression models were used for readmissions. All models were adjusted for age, sex, race, and neighborhood socioeconomic status and included an offset for follow-up time. The results are the percent change and the 95% confidence interval (CI). Results Associations between prescribed fire occurrences and hospital visits were generally null, with the few associations observed being with prescribed fires within 5 and 2 km of the primary residence in the negative direction but not the more restrictive 1 km radius. However, exposure to medium or heavy smoke (primarily from wildfires) at the zip code level was associated with both 7-day (8.5% increase; 95% CI = 1.5%, 16.0%) and 30-day readmissions (5.4%; 95% CI = 2.3%, 8.5%), and to a lesser degree, hospital visits (1.5%; 95% CI: 0.0%, 3.0%) matching previous studies. Conclusions Area-level smoke exposure driven by wildfires is positively associated with hospital utilization but not proximity to prescribed fires.

Raab, Henry↗
DOE OSTI2023

Integration of Nuclear Material Accounting Data and Process Monitoring Data for Improvement on Detection Probability in Safeguarding Electrochemical Processing Facilities (Final Technical Report)

The KAERI advanced spent fuel conditioning process (ACP) process is a critical component of the US- South Korean nuclear cooperation and the following “123 Agreement.” Its development has received considerable attention in both countries. The ACP is an electrochemical processing (pyroprocessing) that recycles over 96% of the used nuclear fuel (UNF). It is also intrinsically proliferation-resistant in theory. In normal operation, the U/TRU product is very hot radiologically. In addition, the Cm provides a high level of spontaneous neutrons, making the product unsuitable for weapon use. However, as pointed in some study, “the need for safeguards to protect against the diversion and misuse of separated plutonium applies essentially equally to all grades of plutonium.” As pointed by many studies, the well-established traditional Nuclear Material Accounting (NMA) approach cannot be directly applied to electrochemical processing because of the lack of an input accountability tank, the non-continuous material flow, and the unsatisfactory level of confidence in sampling methods. Therefore, nuclear safeguards remain a grand challenge in the developing of commercial electrochemical separations facilities, especially around the heart of such facilities, the electrorefiner (ER) systems. In contrast to NMA data, process monitoring (PM) data is normally an indirect measurement of the SNM and is acquired much more frequently. In a broad sense, PM includes monitoring by various types of equipment, e.g. radiation detectors, cameras, voltage, current sensors. Because it is already being collected by the operator, the additional cost to safeguards is low. It has long been believed that PM data can supplement NMA data and help improve safeguards, although the benefits are hard to quantify. The U.S. DOE’s Material Protection, Accounting, and Control Technology (MPACT) campaign has made substantial investments into innovative PM sensor technology and predictive model development for real- or near real-time measurement and prediction of molten salt density and level, salt composition and actinide concentration especially Pu, the cell voltage, and the cell current to supplement traditional NMA. For aqueous-based reprocessing facilities, it is reported that PM, integrated with traditional NMA, have a high detection probability for specific diversions. For electrochemical reprocessing, preliminary studies have shown that PM data can support traditional NMA in various ways by providing a basis to estimate some of the in-processing nuclear material inventories. Despite early success, further studies on fusion of PM data and NMA data are still needed, which is the goal of this proposed work.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

A Nickel-Decorated Carbon Flower/Sulfur Cathode for Lean-Electrolyte Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries involve a reversible conversion reaction between sulfur and lithium sulfide (Li 2 S) via a series of soluble lithium polysulfide intermediates (LiPSs), enabling a high theoretical specific capacity of 1675 mAh g –1 . However, this process exhibits large polarization and low sulfur utilization and suffers critical capacity fade. The primary approach to tackle the problem has so far been to infiltrate sulfur into nanostructured carbon. Furthermore, most studies using porous carbon as host materials have tested with high electrolyte to sulfur ratios (E/S) (generally > 15 µL mg –1 ) that compromise the cell-level energy density. Here, a flower-shaped porous carbon structure with nickel nanoparticles that can address the problems discussed above is designed. First, the 3D flower-shaped carbon structure enables short ionic transport lengths. Second, the small pore diameters <10 nm and high specific surface areas > 3300 m 2 g –1 with sufficient pore volume are ideal for charging performance for low E/S ratios. Finally, Ni nanoparticles are employed onto the flower-shaped network to improve the reaction kinetics. Collectively, it is successfully demonstrated that the batteries with a high mass loading of 5 mg cm –2 and a 5 µL mg –1 E/S ratio can retain cycle retention of 70% after 150 cycles.

25 ENERGY STORAGE↗
DOE OSTI2024

Tri‐Metallic Catalyst for Oxygen Evolution Reaction Enables Continuous Operation of Anion Exchange Membrane Electrolyzer at 1A cm −2 for Hundreds of Hours

Abstract Although numerous efforts are made to synthesize active electrocatalysts for green hydrogen production; catalyst stability, and facile synthesis to scale up the production are still challenging. Herein, the production of novel non‐PGM catalysts for the oxygen reduction reaction (OER) in an alkaline aqueous medium is reported, which is based on the synthesis of a trimetallic metal–organic framework (MOF) precursors. Fine‐tuning of the composition of the metal centers (Ni, Co, and Fe) shows a great effect on OER activity after the MOF undergoes dynamic chemical and structural transformations under OER conditions. In situ characterization reveals the origin of OER activity enhancement as metals’ oxidation state increases, inducing compressive mechanical strain on metal centers, enhancing the electronic conductivity through the formation of oxygen vacancies, and stronger metal–oxygen covalency. Catalysts are used in membrane electrode assembly (MEA) setup within an industrial full‐cell anion exchange membrane electrolyzer (AEMEC), showing a stable performance for 550 h without noticeable decay at 750 and 1000 mA cm −2 industrial level current densities.

Chemistry↗
DOE OSTI2022

High-performance all-solid-state Li–S batteries enabled by an all-electrochem-active prelithiated Si anode

The development of all-solid-state Li–S batteries has been greatly impeded by dendrite growth and dendrite penetration, which are both related to the Li metal anode. As a compromised alternative, we report lithium silicide (Li x Si) as a dendrite-free and high-capacity anode with Li source. Here, the as-synthesized Li x Si is relatively soft, highly electronically conductive, and with a high Li diffusivity. These distinctive properties make Li x Si anode viable as an “all-electrochem-active” electrode (consisted of 100 wt.% Li x Si). Compared with the typical composite electrode, the all-electrochem-active electrode not merely maximizes the electrode-level energy density but also minimizes the electrolyte-related interfacial degradation. Li x Si symmetric cell demonstrates a reversible cycling at 4 mA cm –2 for over 320 h. Stress change and morphological evolution of the Li x Si electrode are investigated upon dealloying/alloying. When paired with a S cathode (active mass loading of 3 mg cm –2 ), Li x Si–S full cell shows a good cycling behavior over 500 cycles and rate performance (69% capacity retained at 1.2C) even at 25 °C.

25 ENERGY STORAGE↗
DOE OSTI2023

Atomically dispersed zeolite-supported rhodium complex: Selective and stable catalyst for acetylene semi-hydrogenation

In this study, supported rhodium catalysts are known to be unselective for semi-hydrogenation reactions. Here, by tuning the electronic structure of supported mononuclear rhodium sites determined by the metal nuclearity and the electron-donor properties of the support, we report that atomically dispersed HY zeolite-supported rhodium with reactive acetylene ligands affords a stable ethylene selectivity > 90 % for acetylene semi-hydrogenation at 373 K and atmospheric pressure, even when ethylene is present in a large excess over acetylene. Infrared and X-ray absorption spectra and measurements of rates of the catalytic reaction complemented with calculations at the level of density functional theory show how the catalyst performance depends on the electronic structure of the rhodium, influenced by the support as a ligand that is a weak electron donor.

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

Divertor heat flux challenge and mitigation in SPARC

Owing to its high magnetic field, high power, and compact size, the SPARC experiment will operate with divertor conditions at or above those expected in reactor-class tokamaks. Power exhaust at this scale remains one of the key challenges for practical fusion energy. Based on empirical scalings, the peak unmitigated divertor parallel heat flux is projected to be greater than 10 GW m -2 . This is nearly an order of magnitude higher than has been demonstrated to date. Furthermore, the divertor parallel Edge-Localized Mode (ELM) energy fluence projections (~11–34 MJ m -2 ) are comparable with those for ITER. However, the relatively short pulse length (~25 s pulse, with a ~10 s flat top) provides the opportunity to consider mitigation schemes unsuited to long-pulse devices including ITER and reactors. The baseline scenario for SPARC employs a ~1 Hz strike point sweep to spread the heat flux over a large divertor target surface area to keep tile surface temperatures within tolerable levels without the use of active divertor cooling systems. In addition, SPARC operation presents a unique opportunity to study divertor heat exhaust mitigation at reactor-level plasma densities and power fluxes. Not only will SPARC test the limits of current experimental scalings and serve for benchmarking theoretical models in reactor regimes, it is also being designed to enable the assessment of long-legged and X-point target advanced divertor magnetic configurations. Experimental results from SPARC will be crucial to reducing risk for a fusion pilot plant divertor design.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Dislocation-Activated Low Platinum-Loaded PtCu Nanoparticles Welded onto the Substrate for Practical Acidic Hydrogen Generation

Although transition metal (M) alloying with platinum (Pt) is a promising approach to reduce the Pt dosage required in the hydrogen evolution reaction (HER), the catalytic activity and durability of PtM alloy are often unsatisfactory for acidic HER, especially at high currents, due to a reduced number of highly active sites (Pt) at the atomic level and challenges in stabilizing them to prevent detachment and aggregation. Herein, we report a robust functional structure integrated electrode (D-PtCu/CF) with abundant edge dislocations and very low platinum content (0.1 mg cm -2 ) to achieve high activity and stability in acidic HER within a proton exchange membrane water electrolysis cell (PEMWE). D-PtCu/CF exhibits high Pt mass activity (10.28 A mg Pt -1 ) and excellent operational stability (negligible decay after 200 h). X-ray absorption spectroscopy and in situ electrochemical experiments reveal that the lattice distortion caused by edge dislocations in PtCu mainly affects Pt atoms by compressing strain, reducing their ability to adsorb H. At the same time, Cu atoms are subjected to tensile strain, enhancing the bonding between Cu and H. Therefore, edge dislocations not only improve the intrinsic catalytic activity of Pt atoms but also increase the number of active sites (Cu) available for hydrogen adsorption, which synergistically accelerates the kinetics of the HER reaction. Finally, the PEMWE employing the D-PtCu/CF catalytic electrode can operate stably for 100 h at an industrial-level current density of 500 mA cm -2 with 1.63 V.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2020

Eutectic Synthesis of the P2-Type Na x Fe 1/2 Mn 1/2 O 2 Cathode with Improved Cell Design for Sodium-Ion Batteries

An engaging area of research in sodium-ion batteries (SIBs) has been focusing on discovery, design, and synthesis of high-capacity cathode materials in order to boost energy density to levels close enough to that of state-of-the-art lithium-ion batteries. Of particular interest, P2-type layered oxide, Na 2/3 Fe 1/2 Mn 1/2 O 2 , has been researched as a potential cathode in SIBs based on its high theoretical capacity of 260 mA h/g and use of noncritical materials. However, the reported synthesis methods are not only complex and energy-demanding but also often yield inhomogeneous and impure materials with capacities less than 200 mA h/g under impractical test conditions. Here, we report a novel synthesis route using low-temperature eutectic reaction to produce highly homogeneous, crystalline, and impurity-free P2-Na x Fe 1/2 Mn 1/2 O 2 with enhanced Na-ion diffusivity and kinetics. The overall electrochemical performances of the Na-ion cells have been improved by pairing the P2-cathode with presodiated hard carbon anodes, leading to reversible capacities in the range of 180 mA h/g. This new approach is a contribution toward the simplification of synthesis and scalability of sodium-based cathodes with high crystallinity and fine-tuned morphology and the realization of a sodium-ion battery system with lower cost and improved electrochemical performance.

25 ENERGY STORAGE↗
DOE OSTI2023

Enhanced Electrochemical Performance of Disordered Rocksalt Cathodes Enabled by a Graphite Conductive Additive

Cobalt-free cation-disordered rocksalt (DRX) cathodes are a promising class of materials for next-generation Li-ion batteries. Although they have high theoretical specific capacities (>300 mA h/g) and moderate operating voltages (~3.5 V vs Li/Li + ), DRX cathodes typically require a high carbon content (up to 30 wt %) to fully utilize the active material which has a detrimental impact on cell-level energy density. To assess pathways to reduce the electrode’s carbon content, the present study investigates how the carbon’s microstructure and loading (10–20 wt %) influence the performance of DRX cathodes with the nominal composition Li 1.2 Mn 0.5 Ti 0.3 O 1.9 F 0.1 . While electrodes prepared with conventional disordered carbon additives (C65 and ketjenblack) exhibit rapid capacity fade due to an unstable cathode/electrolyte interface, DRX cathodes containing 10 wt % graphite show superior cycling performance (e.g., reversible capacities ~260 mA h/g with 85% capacity retention after 50 cycles) and rate capability (~135 mA h/g at 1000 mA/g). Furthermore, a suite of characterization tools was employed to evaluate the performance differences among these composite electrodes. Overall, these results indicate that the superior performance of the graphite-based cathodes is largely attributed to the: (i) formation of a uniform graphitic coating on DRX particles which protects the surface from parasitic reactions at high states of charge and (ii) homogeneous dispersion of the active material and carbon throughout the composite cathode which provides a robust electronically conductive network that can withstand repeated charge–discharge cycles. Overall, this study provides key scientific insights on how the carbon microstructure and electrode processing influence the performance of DRX cathodes. Based on these results, exploration of alternative routes to apply graphitic coatings is recommended to further optimize the material performance.

25 ENERGY STORAGE↗
DOE OSTI2021

Mechanistic Investigation of Molybdenum Disulfide Defect Photoluminescence Quenching by Adsorbed Metallophthalocyanines

Lattice defects play an important role in determining the optical and electrical properties of monolayer semiconductors such as MoS 2 . Although the structures of various defects in monolayer MoS 2 are well studied, little is known about the nature of the fluorescent defect species and their interaction with molecular adsorbates. In this study, the quenching of the low-temperature defect photoluminescence (PL) in MoS 2 is investigated following the deposition of metallophthalocyanines (MPcs). The quenching is found to significantly depend on the identity of the phthalocyanine metal, with the quenching efficiency decreasing in the order CoPc > CuPc > ZnPc, and almost no quenching by metal-free H 2 Pc is observed. Futher, time-correlated single photon counting (TCSPC) measurements corroborate the observed trend, indicating a decrease in the defect PL lifetime upon MPc adsorption, and the gate voltage-dependent PL reveals the suppression of the defect emission even at large Fermi level shifts. Density functional theory modeling argues that the MPc complexes stabilize dark negatively charged defects over luminescent neutral defects through an electrostatic local gating effect. These results demonstrate the control of defectbased excited-state decay pathways via molecular electronic structure tuning, which has broad implications for the design of mixeddimensional optoelectronic devices.

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

Stable Metal–Organic Electrocatalysts for Anion-Exchange Membrane Water Electrolyzers by Defect Engineering

Developing efficient and durable catalysts for the alkaline oxygen evolution reaction (OER) is vital to achieving practical anion-exchange membrane water electrolyzers (AEMWE) for green hydrogen production. In this work, we break the activity-stability trade-off of electrocatalysis by defect engineering of Ni-based metal-organic electrocatalysts (Ni-benzene dicarboxylate; Ni-BDC) through coordinating ferrocenecarboxylates (Fc) to the metal sites. Experimental results collectively reveal that the defect MOF (Ni-BDC:Fc_5:1) exhibits a high OER turnover frequency of 0.75 O 2 s -1 at 300 mV overpotential. Operando Raman spectroscopy and isotope-labelling electrochemical mass spectrometry measurements indicate the structure of Ni-BDC:Fc_5:1 is also more stable in service than that of pure Ni-BDC. The high activity and stability could be attributed to the moderate defects (i.e., unsaturated Ni sites) in the structure that not only increase the intrinsic activity and stability of the local active environment by inhibiting lattice oxygen exchange, but also electrochemically activates the bulk of the catalysts by creating a porous network that facilitates internal H 2 O/OH - conduction with enhanced electronic conduction. Accordingly, an AEMWE employing Ni-BDC:Fc_5:1 as the OER catalyst delivers an industrial-level current density of 1 A cm -2 at 1.73 V cell and can be steadily operated for more than 120 hours.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

In-situ observation of trapped carriers in organic metal halide perovskite films with ultra-fast temporal and ultra-high energetic resolutions

Abstract We in-situ observe the ultrafast dynamics of trapped carriers in organic methyl ammonium lead halide perovskite thin films by ultrafast photocurrent spectroscopy with a sub-25 picosecond time resolution. Upon ultrafast laser excitation, trapped carriers follow a phonon assisted tunneling mechanism and a hopping transport mechanism along ultra-shallow to shallow trap states ranging from 1.72–11.51 millielectronvolts and is demonstrated by time-dependent and independent activation energies. Using temperature as an energetic ruler, we map trap states with ultra-high energy resolution down to < 0.01 millielectronvolt. In addition to carrier mobility of ~4 cm 2 V −1 s −1 and lifetime of ~1 nanosecond, we validate the above transport mechanisms by highlighting trap state dynamics, including trapping rates, de-trapping rates and trap properties, such as trap density, trap levels, and capture-cross sections. In this work we establish a foundation for trap dynamics in high defect-tolerant perovskites with ultra-fast temporal and ultra-high energetic resolution.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Balancing Interfacial Reactions to Achieve Long Cycle Life in High Energy Lithium Metal Batteries

Rechargeable lithium (Li) metal batteries have attracted wide attentions as the next generation energy storage technologies. However, simultaneously achieving high cell-level energy density and long cycle life in realistic batteries is still a great challenge. Here we investigate the cell degradation mechanisms of Li||LiNi0.6Mn0.2Co0.2O2 pouch cells using different, but representative cell configurations to understand the fundamental linkage among Li thickness, electrolyte depletion and the structure evolution of solid electrolyte interphase (SEI) layers. Different cell failure modes were discovered when tuning the anode to cathode capacity (N/P) ratio in compatible electrolyte. With a thick-Li anode (N/P ratio = 2.5), initial stable cycling is obtained because of the abundant Li supply from the anode together with an artificially inflated high Coulombic Efficiency, followed by a premature sudden cell death appears due to the enrichment of “ineffective SEI” which does not participate in the electrochemical reactions but keep increasing cell impedance. The anode-free cell (N/P 0:1) displays a steady capacity decay because cathode Li loss dominates from the beginning to the end of cell cycle life. An optimized thin-Li (N/P 1:1) well balances the Li consumption rate with the impedance buildup by minimizing the growth of ineffective SEI layer, thus decelerates cell polarization increasing and extends cycling. Contrary to conventional wisdoms, long cycle life is observed by using ultra thin-Li (20 µm) in balanced cells. A prototype 350 Wh kg-1 pouch cell (2.0 Ah) achieves over 600 long stable cycles with 76% capacity retention without sudden cell death.

Niu, Chaojiang↗
DOE OSTI2025

Strain engineering of doped hydrogen passivated silicon quantum dots

Silicon quantum dots are nanomaterials that are attractive candidates for photovoltaic applications. Doping of these materials creates p-n junctions and is important for solar cells. In this work, we present a first-principles study of the coupled influence of doping and strain on the stability, energy gap, Fermi level, electronic density, and density of states of hydrogen-passivated silicon quantum dots. We find that the cohesive energy and the energy gap decrease with increasing quantum dot size and are strongly influenced by strain. Furthermore, the response to strain also depends on the size of the quantum dot and dopant type. We present expressions of cohesive energy and energy gap as power-law of size and polynomial dependence on strain. We also show that the Fermi energy increases with size for pristine and p-type doping but decreases with size for n-type doping. We also discuss the influence of strain and dopant type on the density of states and electron density of the quantum dots.

77 NANOSCIENCE AND NANOTECHNOLOGY↗