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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 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Boosting Sodium Storage in TiO 2 Nanotube Arrays through Surface Phosphorylation

In this paper, sodium–ion batteries (SIBs) offer a promise of a scalable, low–cost, and environmentally benign means of renewable energy storage. However, the low capacity and poor rate capability of anode materials present an unavoidable challenge. In this work, it is demonstrated that surface phosphorylated TiO 2 nanotube arrays grown on Ti substrate can be efficient anode materials for SIBs. Fabrication of the phosphorylated nanoarray film is based on the electrochemical anodization of Ti metal in NH 4 F solution and subsequent phosphorylation using sodium hypophosphite. The phosphorylated TiO 2 nanotube arrays afford a reversible capacity of 334 mA h g –1 at 67 mA g –1 , a superior rate capability of 147 mA h g –1 at 3350 mA g –1 , and a stable cycle performance up to 1000 cycles. In situ X–ray diffraction and transmission electron microscopy reveal the near–zero strain response and robust mechanical behavior of the TiO 2 host upon (de)sodiation, suggesting its excellent structural stability in the Na+ storage application.

25 ENERGY STORAGE↗
DOE OSTI2014

Deep-red semiconductor monolithic mode-locked lasers

A deep-red semiconductor monolithic mode-locked laser is demonstrated. Multi-section laser diodes based on an AlGaAs multi-quantum-well structure were passively mode-locked, enabling the generation of picosecond optical pulses at 752 nm, at pulse repetition rates of 19.37 GHz. An investigation of the dependence of the pulse duration as a function of reverse bias revealed a predominantly exponential decay trend of the pulse duration, varying from 10.5 ps down to 3.5 ps, which can be associated with the concomitant reduction of absorption recovery time with increasing applied field. A 30-MHz-tunability of the pulse repetition rate with bias conditions is also reported. The demonstration of such a compact, efficient and versatile ultrafast laser in this spectral region paves the way for its deployment in a wide range of applications such as biomedical microscopy, pulsed terahertz generation as well as microwave and millimeter-wave generation, with further impact on sensing, imaging and optical communications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Porous Two-dimensional Iron-Cyano Nanosheets for High-rate Electrochemical Nitrate Reduction

Ammonia (NH 3 ) is an essential ingredient in agriculture and a promising source of clean energy as a hydrogen carrier. The current major method for ammonia production, however, is the Haber–Bosch process that leads to massive energy consumption and severe environmental issues. Compared with nitrogen (N 2 ) reduction, electrochemical nitrate reduction reaction (NO 3 RR), with a higher NH 3 yield rate and Faradaic efficiency, holds promise for efficient NH 3 production under ambient conditions. To achieve efficient NO 3 RR, electrocatalysts should exhibit high selectivity and Faradaic efficiency with a high NH 3 yield rate. In this work, we developed two-dimensional (2D) iron-based cyano-coordination polymer nanosheets (Fe-cyano NSs) following in situ electrochemical treatment for high-rate NO 3 RR. Owing to the strong adsorption of nitrate on Fe0 active sites generated via topotactic conversion and in situ electroreduction, 2D Fe-cyano electrocatalyst exhibits high catalytic activity with a yield rate of 42.1 mg h –1 mgcat –1 and a Faradaic efficiency of over 90% toward NH 3 production at –0.5 V (vs reversible hydrogen electrode, RHE). Further electrochemical characterizations revealed that superhydrophilic surface and enhanced electrochemical surface area of the 2D porous nanostructures also contributed to the high-rate NO 3 RR activity. Finally, an electrolyzer toward NO 3 RR and oxygen evolution reaction (OER) in a two-electrode configuration is constructed based on 2D Fe-cyano, achieving an energy efficiency of 26.2%. This work provides an alternative methodology toward topotactic conversion of transition metal nanosheets for NO 3 RR and reveals the often-overlooked contribution of hydrophilicity of the catalysts for high-rate electrocatalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Electrochemical and Spectroscopic Analysis of Mg2+ Intercalation into Thin Film Electrodes of Layered Oxides: V2O5 and MoO3

Electrochemical, surface, and structural studies related to rechargeable Mg batteries were carried out with monolithic thin-film cathodes comprising layered V2O5 and MoO3. The reversible intercalation reactions of these electrodes with Mg ion in nonaqueous Mg salt solutions were explored using a variety of analytical tools. These included slow-scan rate cyclic voltammetry (SSCV), chrono-potentiometry (galvanostatic cycling), Raman and photoelectron spectroscopies, high-resolution microscopy, and XRD. The V2O5 electrodes exhibited reversible Mg-ion intercalation at capacities around 150-180 mAh g(-1) with 100% efficiency. A capacity of 220 mAh g(-1) at >95% efficiency was obtained with MoO3 electrodes. By applying the electrochemical driving force sufficiently slowly it was possible to measure the electrodes at equilibrium conditions and verify by spectroscopy, microscopy, and diffractometry that these electrodes undergo fully reversible structural changes upon Mg-ion insertion/deinsertion cycling.

Gershinsky, G↗
DOE OSTI2024

Calibration and validation of the foundation for a multiphase strength model for tin

In this work, the Common Model of Multi-phase Strength and Equation of State (CMMP) model was applied to tin. Specifically, calibrations of the strength-specific elements of the CMMP foundation were developed with a combination of experiments and theory, and then the model was validated experimentally. The first element of the foundation is a multi-phase analytic treatment of the melt temperature and the shear modulus for the solid phases. These models were parameterized for each phase based on ab initio calculations using the software VASP (Vienna Ab initio Simulations Package) based on density functional theory. The shear modulus model for the ambient phase was validated with ultrasonic sound speed measurements as a function of pressure and temperature. The second element of the foundation is a viscoplastic strength model for the phase, upon which strength for inaccessible higher-pressure phases can be scaled as necessary. The stress–strain response of tin was measured at strain rates of 10 -3 to 3 x 10 3 s -1 and temperatures ranging from 87 to 373 K. The Preston–Tonks–Wallace (PTW) strength model was fit to that data using Bayesian model calibration. For validation, six forward and two reverse Taylor impact experiments were performed at different velocities to measure large plastic deformation of tin at strain rates up to ⁠10 5 s -1 . The PTW model accurately predicted the deformed shapes of the cylinders, with modest discrepancies attributed to the inability of PTW to capture the effects of twinning and dynamic recrystallization. Some material in the simulations of higher velocity Taylor cylinders reached the melting temperature, thus testing the multiphase model because of the presence of a second phase, the liquid. In simulations using a traditional modeling approach, the abrupt reduction of strength upon melt resulted in poor predictions of the deformed shape and non-physical temperatures. With CMMP, the most deformed material points evolved gradually to a mixed solid–liquid but never a fully liquid state, never fully lost strength, stayed at the melt temperature as the latent heat of fusion was absorbed, and predicted the deformed shape well.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Structural Changes and Reversibility Upon Deintercalation of Li from LiCoPO 4 Derivatives

In an effort to improve the cycle life and rate capability of olivine LiCoPO 4 , Cr, Fe, and Si were added to produce nominal Li 1.025 Co 0.84 Fe 0.10 Cr 0.05 Si 0.01 (PO 4 ) 1.025 . This cathode material has an energy density comparable to LiCoPO 4 , with markedly improved electrochemical performance. Here, we apply operando X-ray diffraction to gain an understanding of the crystallographic delithiation mechanism of this new substituted electrode material, compared to both LiCo 0.75 Fe 0.25 PO 4 and LiCo 0.75 Fe 0.25 PO 4 . Throughout charging, the extent of solid-solution domains was significantly increased in Li 1.025 Co 0.84 Fe 0.10 Cr 0.05 Si 0.01 (PO 4 ) 1.025 and LiCo 0.75 Fe 0.25 PO 4 compared to LiCoPO 4 . These domains reduce the mechanical strain during electrode function, providing a clear explanation for the high durability with Co substitution. Li 1.025 Co 0.84 Fe 0.10 Cr 0.05 Si 0.01 (PO 4 ) 1.025 operated at notably higher average potential than LiCo 0.75 Fe 0.25 PO 4 , which would increase the energy density of the cell. Ex situ measurements reveal the persistence of structural irreversibilities in the substituted phase after the first cycle, identifying avenues for further improvement in durability. Overall, this finding sheds light on the strategies for judicious cation substitution in LiCoPO 4 electrodes to maximize the cycle life while preserving high energy density, especially compared to LiFePO 4 .

25 ENERGY STORAGE↗
DOE OSTI2024

Calibration and validation of the foundation for a multiphase strength model for tin

In this work, the Common Model of Multi-phase Strength and Equation of State (CMMP) model was applied to tin. Specifically, calibrations of the strength-specific elements of the CMMP foundation were developed with a combination of experiments and theory, and then the model was validated experimentally. The first element of the foundation is a 10 multi-phase analytic treatment of the melt temperature and the shear modulus for the solid phases. These models were parameterized for each phase based on ab initio calculations using the software VASP (Vienna Ab initio Simulations Package) based on density functional theory (DFT). The shear modulus model for the ambient β phase was validated with ultrasonic sound speed measurements as a function of pressure and temperature. The second element of the foundation is a viscoplastic strength model for the β phase, upon which strength for inaccessible higher-pressure phases can be scaled as necessary. The stress-strain response of tin was measured at strain rates of 10 -3 to 3 x 10 3 s -1 and temperatures ranging from 87 to 373 K. The Preston-Tonks-Wallace (PTW) strength model was fit to that data using Bayesian model calibration. For validation, six forward and two reverse Taylor impact experiments were performed at different velocities to measure large plastic deformation of tin at strain rates up to 10 5 s -1 . The PTW model accurately predicted the deformed shapes of the cylinders, with modest discrepancies attributed to the inability 20 of PTW to capture the effects of twinning and dynamic recrystallization. Some material in the simulations of higher velocity Taylor cylinders reached the melting temperature, thus testing the multiphase model because of the presence of a second phase, the liquid. In simulations using a traditional modeling approach, the abrupt reduction of strength upon melt resulted in poor predictions of the deformed shape and non-physical temperatures. With CMMP, the most deformed material points evolved gradually to a mixed solid-liquid but never fully liquid state, never fully lost strength, 25 stayed at the melt temperature as the latent heat of fusion was absorbed, and predicted the deformed shape well.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Non-topotactic reactions enable high rate capability in Li-rich cathode materials

High-rate cathode materials for Li-ion batteries require fast Li transport kinetics, which typically rely on topotactic Li intercalation/de-intercalation because it minimally disrupts Li transport pathways. In contrast to this conventional view, here we demonstrate that the rate capability in a Li-rich cation-disordered rocksalt cathode can be significantly improved when the topotactic reaction is replaced by a non-topotactic reaction. The fast non-topotactic lithiation reaction is enabled by facile and reversible transition metal octahedral-to-tetrahedral migration, which improves rather than impedes Li transport. Using this concept, we show that high-rate performance can be achieved in Mn- and Ni-based cation-disordered rocksalt materials when some of the transition metal content can reversibly switch between octahedral and tetrahedral sites. Overall, this study provides a new perspective on the design of high-performance cathode materials by demonstrating how the interplay between Li and transition metal migration in materials can be conducive to fast non-topotactic Li intercalation/de-intercalations.

25 ENERGY STORAGE↗
NASA NTRS1986

High temperature monotonic and cyclic deformation in a directionally solidified nickel-base superalloy

Directionally solidified (DS) MAR-M246+Hf was tested in tension and fatigue, at temperatures from 20 C to 1093 C. Tests were performed on (001) oriented specimens at strain rates of 50 % and 0.5 % per minute. In tension, the yield strength was constant up to 704 C, above which the strength dropped off rapidly. A strong dependence of strength on strain rate was seen at the higher temperatures. The deformation mode was observed to change from heterogeneous to homogeneous with increasing temperature. Low Cycle Fatigue tests were done using a fully reversed waveform and total strain control. For a given plastic strain range, lives increased with increasing temperature. For a given temperature strain rate had a strong effect on life. At 704 C, decreasing strain rates decreased life, while at the higher temperatures, decreasing strain rates increased life, for a given plastic strain range. These results could be explained through considerations of the deformation modes and stress levels. At the higher temperatures, marked coarsening caused beneficial stress reductions, but oxidation limited the life. The longitudinal grain boundaries were found to influence slip behavior. The degree of secondary slip adjacent to the boundaries was found to be related to the degree of misorientation between the grains.

Huron, Eric S.↗
DOE OSTI2024

Fully Scalable Randomized Benchmarking Without Motion Reversal

We introduce , a protocol that streamlines traditional RB by using circuits consisting almost entirely of independent identically distributed (IID) layers of gates. BiRB reliably and efficiently extracts the average error rate of a Clifford gate set by sending tensor-product eigenstates of random Pauli operators through random circuits with IID layers. Unlike existing RB methods, BiRB does not use motion reversal circuits—i.e., circuits that implement the identity (or a Pauli) operator—which simplifies both the method and the theory proving its reliability. Furthermore, this simplicity enables scaling BiRB to many more qubits than the most widely used RB methods. Published by the American Physical Society 2024

Hines, Jordan (ORCID:0000000151267256)↗
DOE OSTI2015

Beyond Yolk–Shell Nanoparticles: Fe 3 O 4 @Fe 3 C Core@Shell Nanoparticles as Yolks and Carbon Nanospindles as Shells for Efficient Lithium Ion Storage

In order to well address the problems of large volume change and dissolution of Fe 3 O 4 nanomaterials during Li + intercalation/extraction, herein we demonstrate a one-step in situ nanospace-confined pyrolysis strategy for robust yolk–shell nanospindles with very sufficient internal void space (VSIVS) for high-rate and long-term lithium ion batteries (LIBs), in which an Fe 3 O 4 @Fe 3 C core@shell nanoparticle is well confined in the compartment of a hollow carbon nanospindle. This structure can not only introduce VSIVS to accommodate volume change of Fe 3 O 4 but also afford a dual shell of Fe 3 C and carbon to restrict Fe 3 O 4 dissolution, thus providing dual roles for greatly improving the capacity retention. Consequently, Fe 3 O 4 @Fe 3 C–C yolk–shell nanospindles deliver a high reversible capacity of 1128.3 mAh g –1 at even 500 mA g –1 , excellent high rate capacity (604.8 mAh g –1 at 2000 mA g – 1), and prolonged cycling life (maintaining 1120.2 mAh g –1 at 500 mA g –1 for 100 cycles) for LIBs, which are much better than those of Fe 3 O 4 @C core@shell nanospindles and Fe 3 O 4 nanoparticles. The present Fe 3 O 4 @Fe 3 C–C yolk–shell nanospindles are the most efficient Fe 3 O 4 -based anode materials ever reported for LIBs.

25 ENERGY STORAGE↗
DOE OSTI2021

Oxygen redox chemistry in P2-Na 0.6 Li 0.11 Fe 0.27 Mn 0.62 O 2 cathode for high-energy Na-ion batteries

Owing to the abundance of raw material reserves and low cost, Na-ion batteries (NIBs) have successfully gained widespread attention from academic and industrial communities in the past few decades. However, the insufficient cathode energy density is still one of the critical bottlenecks restricting the development of NIBs. Following a strategy of introducing Li+ into the transition-metal (TM) layer to enhance the oxygen redox reaction, a novel layered cathode material P2-Na 0.6 Li 0.11 Fe 0.27 Mn 0.62 O 2 (NLFMO) was designed and successfully synthesized. This NLFMO cathode not only delivers a large initial reversible capacity of 207.3 mA h g -1 , but also shows a good cycling performance (104.2 mA h g -1 after 80 cycles) and rate capability (126.2 mA h g -1 at 1C). The ultrahigh capacity is contributed by both cationic (Fe 3+ /Fe 4+ and Mn 3+ /Mn 4+ ) and partially reversible anionic redox (O 2- /O n- ) reactions, revealed by in situ X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) techniques. Moreover, no detrimental P2–O2 phase transition was observed in ex situ X-ray diffraction (XRD) patterns, confirming the high structural stability during Na + deintercalation/intercalation processes. These results provide valuable information about the high-energy density layered cathode materials based on anionic redox reactions for NIBs.

25 ENERGY STORAGE↗
DOE OSTI2019

Conversion of acenaphthalene to phenalene via methylation: A theoretical study

Ab initio calculations of the C 13 H 10 and C 13 H 9 potential energy surfaces related to the reaction of 1-acenaphthyl and methyl radicals and secondary isomerization of C 13 H 9 primary radical products have been performed at the chemically accurate G3(MP2,CC)//B3LYP/6-311G** level of theory to unravel the mechanism of conversion of acenaphthalene to phenalene or phenalenyl radical + H. The computed energetics and molecular parameters were utilized in Rice-Ramsperger-Kassel-Marcus Master Equation (RRKM-ME) calculations of reaction rate constants and relative product yields. The 1-acenaphthyl + CH 3 reaction is predicted to proceed by a fast radical-radical recombination mechanism and to predominantly produce collisionally stabilized 1-methylacenaphthalene B1 or a C 13 H 9 benzylic radical A1 + H with exothermicities of 106.8 and 25.2 kcal/mol, respectively. The A1 + H channel is preferable at higher temperatures, whereas the stabilization of 1-methylacenaphthalene is favored at higher pressures. The radical A1 can nearly irreversibly interconvert to phenalenyl radical AP via a 22.7 kcal/mol exothermic isomerization process involving formal insertion of the CH 2 group into a C-C bond of the five-member ring leading to the expansion of this ring to a six-member ring. The rate constants for the H addition reaction to phenalenyl radical to form phenalene and the reverse H loss from phenalene were also computed and the strength of the weakest C-H bond in the CH 2 group of phenalene is evaluated as 62.2 kcal/mol. The analysis of the reaction kinetics allowed us to deduce a mechanism for the conversion of 1-acenaphthyl radical to phenalene or phenalenyl radical + H via methylation involving the formation of A1 via a well-skipping channel or stabilization and dissociation of (or H abstraction from) B1 followed by isomerization of A1 to phenalenyl AP, which can add an H atom producing phenalene. As a result, rate constants for the significant elementary reactions are fitted to modified Arrhenius expressions and are proposed for kinetic modeling of the expansion of a five-member ring on a zigzag edge of PAH to a six-member ring by methylation.

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

Ultralow-Strain Zn-Substituted Layered Oxide Cathode with Suppressed P2–O2 Transition for Stable Sodium Ion Storage

Layered transition metal oxides have drawn much attention as a promising candidate cathode material for sodium-ion batteries. However, their performance degradation originating from strains and lattice phase transitions remains a critical challenge. Herein, a high-concentration Zn-substituted Na x MnO 2 cathode with strongly suppressed P2–O2 transition is investigated, which exhibits a volume change as low as 1.0% in the charge/discharge process. Additionally, such ultralow strain characteristics ensure a stable host for sodium ion storage, which significantly improves the cycling stability and rate capability of the cathode material. Also, the strong coupling between the highly reversible capacity and the doping content of Zn in Na x MnO 2 is investigated. It is suggested that a reversible anionic redox reaction can be effectively triggered by Zn ions and is also highly dependent on the Zn content. Such an ion doping strategy could shed light on the design and construction of stable and high-capacity sodium ion host.

25 ENERGY STORAGE↗
DOE OSTI2023

Electrochemical properties of Gd(III) ions in LiCl-KCl-GdCl 3 at 723–1023 K

Electrochemical behavior of Gd(III) ions in molten LiCl-KCl-GdCl 3 was investigated at 723–1023 K via cyclic voltammetry using tungsten as a working electrode, Gd-Bi (mole fraction, x Gd = 0.16) as a reference electrode, and Gd-Bi (x Gd = 0.02) as a counter electrode. A single reduction–oxidation wave was observed, confirming a single-step, 3-electron transfer Gd(III)/Gd transition. The cathodic peak potential exhibited minimal change (<13 mV) over a wide range of scan rates (0.05–0.30 V s –1 ), indicating facile charge transfer kinetics (i.e., a reversible electrode process). A nucleation overpotential associated with solid Gd deposition was observable at low temperatures (T < 823 K). The mass transport properties of Gd(III) ions were estimated using the Berzins and Delahay relation based on diffusion-limiting peak current. The diffusivity values were determined to be D Gd(III) = 0.5–2.7 × 10 –5 cm 2 s –1 at 723–1023 K with an associated activation energy of E a = 33.9 (±1.0) kJ mol –1 . Finally, the two-phase [liquid + GdBi] Gd-Bi alloy reference electrode experienced less than 0.5 mV of drift over 5 days of repeated electrochemical measurements, indicating high stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗