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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 OSTI2020

Interlayer gap widened $α$-phase molybdenum trioxide as high-rate anodes for dual-ion-intercalation energy storage devices

Employing high-rate ion-intercalation electrodes represents a feasible way to mitigate the inherent trade-off between energy density and power density for electrochemical energy storage devices, but efficient approaches to boost the charge-storage kinetics of electrodes are still needed. Here, we demonstrate a water-incorporation strategy to expand the interlayer gap of α-MoO 3 , in which water molecules take the place of lattice oxygen of α-MoO 3 . Accordingly, the modified α-MoO 3 electrode exhibits theoretical-value-close specific capacity (963 C g –1 at 0.1 mV s –1 ), greatly improved rate capability (from 4.4% to 40.2% at 100 mV s –1 ) and boosted cycling stability (from 21 to 71% over 600 cycles). A fast-kinetics dual-ion-intercalation energy storage device is further assembled by combining the modified α-MoO 3 anode with an anion-intercalation graphite cathode, operating well over a wide discharge rate range. Our study sheds light on a promising design strategy of layered materials for high-kinetics charge storage.

25 ENERGY STORAGE↗
DOE OSTI2024

Supramolecular assembly of polycation/mRNA nanoparticles and in vivo monocyte programming

Size-dependent phagocytosis is a well-characterized phenomenon in monocytes and macrophages. However, this size effect for preferential gene delivery to these important cell targets has not been fully exploited because commonly adopted stabilization methods for electrostatically complexed nucleic acid nanoparticles, such as PEGylation and charge repulsion, typically arrest the vehicle size below 200 nm. Here, we bridge the technical gap in scalable synthesis of larger submicron gene delivery vehicles by electrostatic self-assembly of charged nanoparticles, facilitated by a polymer structurally designed to modulate internanoparticle Coulombic and van der Waals forces. Specifically, our strategy permits controlled assembly of small poly(β-amino ester)/messenger ribonucleic acid (mRNA) nanoparticles into particles with a size that is kinetically tunable between 200 and 1,000 nm with high colloidal stability in physiological media. We found that assembled particles with an average size of 400 nm safely and most efficiently transfect monocytes following intravenous administration and mediate their differentiation into macrophages in the periphery. When a CpG adjuvant is co-loaded into the particles with an antigen mRNA, the monocytes differentiate into inflammatory dendritic cells and prime adaptive anticancer immunity in the tumor-draining lymph node. This platform technology offers a unique ligand-independent, particle-size-mediated strategy for preferential mRNA delivery and enables therapeutic paradigmsviamonocyte programming.

Science & Technology - Other Topics↗
DOE OSTI2020

Stabilizing Zinc Anode Reactions by Polyethylene Oxide Polymer in Mild Aqueous Electrolytes

Abstract Zn dendrites growth and poor cycling stability are significant challenges for rechargeable aqueous Zn batteries. Zn metal deposition‐dissolution in aqueous electrolytes is typically determined by Zn anode–electrolyte interfaces. In this work, the role of a long‐chain polyethylene oxide (PEO) polymer as a multifunctional electrolyte additive in stabilizing Zn metal anodes is reported. PEO molecules suppress Zn 2+ ion transfer kinetics and regulate Zn 2+ ion concentration in the vicinity of Zn anodes through interactions between ether groups of PEO and Zn 2+ ions. The suppressed Zn 2+ ion transfer kinetics and homogeneous Zn 2+ ion distribution at the interface promotes dendrite‐free homogeneous Zn deposition. In addition, electrochemically inert PEO molecules adsorbed onto Zn anodes can protect the anode surfaces from H 2 generation and, thereby, enhance their electrochemical stability. Stable cycling over 3000 h and high reversibility (Coulombic efficiency > 99.5%) of Zn anodes is demonstrated in 1 m ZnSO 4 electrolyte with 0.5 wt% PEO. This finding provides helpful insights into the mechanism of Zn metal anodes stabilization by low‐cost multifunctional polymer electrolyte additives that stabilize interfacial reactions.

Jin, Yan↗
DOE OSTI2024

Densification of Cathode/Electrolyte Interphase to Enhance Reversibility of LiCoO 2 at 4.65 V

For LiCoO 2 (LCO) operated beyond 4.55 V (vs Li/Li + ), it usually suffers from severe surface degradation. Constructing a robust cathode/electrolyte interphase (CEI) is effective to alleviate the above issues, however, the correlated mechanisms still remain vague. Herein, a progressively reinforced CEI is realized via constructing Zr-O deposits (ZrO 2 and Li 2 ZrO 3 ) on LCO surface (i.e., Z-LCO). Upon cycle, these Zr-O deposits can promote the decomposition of LiPF6, and progressively convert to the highly dispersed Zr-O-F species. In particular, the chemical reaction between LiF and Zr-O-F species further leads to the densification of CEI, which greatly reinforces its toughness and conductivity. Further, combining the robust CEI and thin surface rock-salt layer of Z-LCO, several benefits are achieved, including stabilizing the surface lattice oxygen, facilitating the interface Li + transport kinetics, and enhancing the reversibility of O3/H1-3 phase transition, etc. As a result, the Z-LCO||Li cells exhibit a high capacity retention of 84.2% after 1000 cycles in 3–4.65 V, 80.9% after 1500 cycles in 3–4.6 V, and a high rate capacity of 160 mAh g -1 at 16 C (1 C = 200 mA g -1 ). This work provides a new insight for developing advanced LCO cathodes.

25 ENERGY STORAGE↗
DOE OSTI2021

Role of thermo-mechanical gyrations on the α/β interface stability in a Ti6Al4V AM alloy

Fluctuating energy distributions experienced during Additive Manufacturing yield an evolution of spatial and temporal transients within a part. In general, the in-situ monitoring of these transients is near to impossible during manufacturing. In order to then gain perspective into the impact on these localized thermo-mechanical transients on the interface stability, rapid thermo-mechanical reversals with known boundary conditions are imposed on an AM Ti6Al4V alloy which resulted in a phase transformation leading to an increased β phase stability. Our goal with this study is to comprehend the kinetics of this phase transformation with concepts of stored energy due to plastic strain accumulation and diffusion kinetics. Atom Probe Tomography is employed to study the partitioning of the solute elements across the interface. As expected, the thermo-mechanically cycled samples showed a reduced Vanadium concentration across the β phase. Finally, this concentration profile across the interface, alongside a full-width-half-max analysis, provided insight on the potential phase transformation kinetics involved in the α → β transformation subject to thermo- mechanical gyrations.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Trifluoromethylated Phenanthroline Ligands Reduce Excited-State Distortion in Homoleptic Copper(I) Complexes

Herein, we report the synthesis and excited-state dynamics for a series of homoleptic copper(I) trifluoromethylated phenanthroline complexes with two, three, and four trifluoromethyl functional groups. Our analysis of the steady-state absorbance and emission, transient-absorption spectroscopy, and electronic-structure-theory calculations results enable in-depth analysis of the pseudo-Jahn–Teller distortion inhibition from increased steric hindrance of the trifluoromethyl functional group relative to the prototypical dimethyl phenanthroline complex. Surprisingly, our results demonstrate that the greatest degree of pseudo-Jahn–Teller distortion inhibition is achieved with trifluoromethylation of only the 2 and 9 positions by an unusual combination of steric hindrance and stabilization of a nondistorted 1 MLCT manifold observed by transient kinetic lifetimes and optimized excited-state structures. The intersystem-crossing (ISC) lifetime for the 2,9-bis(trifluoromethyl)-1,10-phenanthroline Cu(I) complex is 69 ps, while the triplet excited-state lifetime and emission quantum yield are 106 ns and 4 × 10 –3 , respectively. Further trifluoromethylation of the phenanthroline yields a greater σ bond inductive withdrawing force on the phenanthroline nitrogens, ultimately resulting in weaker coordination to the copper. Last, the surprising success of the 2,9-bis(trifluoromethyl)-1,10-phenanthroline Cu(I) complex by adjusting both ligand sterics and electronic properties outlines a new strategy for developing long-lived Cu(I) charge-transfer complexes.

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

4-Electron Oxygen Reduction Reaction (ORR) with Iron Phthalocyanine (FePc) Functionalized Nanowire Templated-3D Fuzzy Graphene (NT-3DFG)

Iron phthalocyanine (FePc) is a promising alternative to platinum-based catalysts for sustainable energy devices; however, the plane-symmetry of Fe-N 4 sites, random aggregation, and poor conductivity of FePc present major barriers for their application as oxygen reduction reaction (ORR) electrocatalysts. Here, we report the synergistic effects of FePc electrocatalysts supported by a nanowire-templated three-dimensional fuzzy graphene (FePc@NT-3DFG) substrate. The in situ functionalized oxygen groups (iFOGs) at the edge of NT-3DFG localize Fe active sites in FePc under alkaline ORR conditions. With a uniform FePc distribution through many single layers of graphene, the NT-3DFG substrates improve O 2 adsorption and catalytic activity while stabilizing the electrochemical activity during reactions. The FePc@NT-3DFG catalyst exhibits fast ORR kinetics with an extremely low Tafel slope of 28.3 ± 2.7 mV dec −1 , a higher half-wave potential of 0.911 ± 0.004 V (vs RHE), and notable long-term stability at 0.5 V (vs RHE) of 96.0 ± 0.4% retention after 30 h. Surface chemistry spectra validate electronic configuration modification of Fe at the iFOGs. Density functional theory calculations indicate that the extra layers of graphene improve oxygen adsorption. Moreover, additional exploration of other transition metal phthalocyanines supports the effects of iFOGs through the transition toward 4e − ORR. This work offers an expanded strategy for active site modification through edge-based graphene substrates for 4e − ORR.

X-ray absorption spectroscopy↗
DOE OSTI2026

Chemical and Structural Insights into Solid Electrolyte Interphase Evolution for Sodium Metal Electrodes

The solid electrolyte interphase (SEI) critically governs the reversibility of sodium metal batteries, through dynamically mediating ion transport and interfacial reactions. However, its kinetic evolution under operating conditions, and how it influences interfacial stability, remains poorly understood. Here, in this study, we reveal that the SEI undergoes coupled chemical and mechanical changes during sodium plating and stripping, leading to spatial and temporal heterogeneity that drives interfacial degradation. Synchrotron operando grazing-incidence wide-angle X-ray scattering and soft X-ray absorption spectroscopy capture the sequential formation and dissolution of inorganic SEI phases (NaF, NaH, NaOH, Na 2 PO 3 F), accompanied by depth-dependent alterations in organic SEI components. Mesoscale modeling connects this evolving SEI heterogeneity to localized current density fluctuations and stress accumulation at the Na interface, identifying pathways to electrically isolated sodium formation. These findings show that SEI instability fundamentally limits reversibility in sodium metal batteries, and that controlling SEI chemistry–mechanics coupling is essential to achieving its durability.

36 MATERIALS SCIENCE↗
DOE OSTI2020

LixNiO/Ni Heterostructure with Strong Basic Lattice Oxygen Enables Electrocatalytic Hydrogen Evolution with Pt-like Activity

The low-cost hydrogen production from water electrolysis is crucial for practical deployment of sustainable hydrogen economy, but is often constrained by the lack of active and robust electrocatalysts from Earth-abundant materials. We describe here an unconventional heterostructure composed of strongly coupled Ni-deficient LixNiO nanoclusters and polycrystalline Ni nanocrystals, and its exceptional activities toward hydrogen evolution reaction (HER) in aqueous electrolytes. The presence of unique lattice oxygen species with strong Brønsted basicity is a significant feature, which spontaneously split water molecules and effectively accelerate the sluggish Volmer H-OH dissociation step in neutral and alkaline HER. In combination with the unpreceded level of intimate LixNiO and Ni interfacial junctions that produces abundant “hotspots” for promoted hydride coupling, the catalyst exhibited kinetic activities almost identical as Pt/C and decent long term stability in universal pH.

Lu, Ke↗
DOE OSTI2025

Single-Electron Transfer Stabilizes Metastable Alane in a Bipyridine-Functionalized MOF Nanopore

Nanoconfinement of metastable hydrides such as alane (AlH 3 ) in functionalized porous frameworks represents a promising yet largely untapped strategy for high-capacity energy storage. Despite its potential, the underlying mechanisms responsible for the thermodynamic stabilization of metastable hydrides are poorly understood. Here, in this study, concepts from solution Lewis acid–base chemistry were applied to a crystalline metal–organic framework (MOF) to stabilize AlH 3 . The long-range order and synthetically versatile pore chemistry enabled us to reveal the intimate details of the hydride-host interactions. Powder X-ray diffraction (PXRD) of AlH 3 -infiltrated UiO-67bpy (Zr 6 O 4 (OH) 4 (bpydc) 6 ; bpydc 2– = 2,2′-bipyridine-5,5′-dicarboxylate) confirms that the framework maintains its crystallinity up to 250 °C and is stable under 70 MPa H 2 pressure. We find that thermodynamic stabilization arises from coupled single-electron and hydrogen-atom transfer from AlH 3 to bipyridine-containing linkers. Electron paramagnetic resonance detects a bipyridyl radical with an anisotropic g-tensor (g values of 2.00132, 2.00215, and 2.00275), consistent with Bader charge analysis predicting 0.82 e – transferred from the hydride to the MOF. These findings establish critical structure–property relationships underpinning AlH 3 stabilization and suggest general strategies for tuning the thermodynamics and kinetics of metastable materials.

Shivanna, Mohana [Sandia National Laboratories (SN↗
DOE OSTI2022

Importance of interface open circuit potential on aqueous hydrogenolytic reduction of benzyl alcohol over Pd/C

Abstract The open circuit potential (OCP) established by the quasi-equilibrated electrode reaction of H 2 and H 3 O + (hydr.) , complicates catalytic reactions significantly. The hydrogenolysis rate of benzylic alcohol on Pd/C increases 2-3 orders of magnitude with the pH decreasing from 7 to 0.6. The reaction follows a pathway of protonated benzyl alcohol dehydration to a benzylic carbenium ion, followed by a hydride addition to form toluene. The dehydration of protonated benzyl alcohol is kinetic relevent, thus, being enhanced at lower pH. The OCP stabilizes all cationic species in the elementary steps. Particularly, the initial state (benzyl alcohol oxonium ion) is less stabilized than the dehydration transition state and the product (benzylic carbenium), thus, lowering the free energy barrier of the rate-determining step. In accordance, the rate increased with increasingly negative OCP. Beside OCP, an external negative electric potential in an electrocatlaytic system was also demonstrated to enhance the rate in the same way.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Understanding the L-H isotope effect at the DIII-D tokamak and advancements in synthetic turbulence diagnostics

Abstract It is determined that while heat flux differences between hydrogen and deuterium isotope experiments result from natural differences in carbon impurity content at DIII-D, it is not the origin of the low to high confinement mode (L-H) transition isotope effect. More specifically, a two times larger edge radial electric field in hydrogen compared to deuterium is uncovered and believed to play an important role. The origin of this radial electric field difference is determined to have two possible origins: differences in poloidal rotation and turbulent Reynolds stress in the closed field line region, and increased outer strike point temperatures and space potentials on open field lines. Experimental observations from both profile and turbulence diagnostics are supported by nonlinear gyrokinetic simulations using the code CGYRO. Simulations illustrated heat transport isotope effects in the plasma edge and shear layer resulting from differences in impurity content, electron non-adiabaticity, and main ion mass dependent E × B shear stabilization. Turbulence prediction comparisons from flux-matched CGYRO simulations to experimental measurements including electron temperature, density and velocity fluctuations are found to be in good agreement with available data. A dedicated DIII-D experiment in hydrogen was performed to seed more carbon than naturally occurring, to match deuterium experiments, and possibly reduce the L-H power threshold based on gyro-kinetic predictions. To our surprise, while ion temperature gradient (ITG) turbulence was stabilized, nodiscernible change in L-H power threshold were observed in these special hydrogen experiments. In particular, it is noticed that the edge radial electric field and Reynolds stress were observed as nearly unchanging in the presence of ITG stabilization. These experimental data have enabled a more comprehensive picture of the multitude of isotope effects at play in fusion experiments, and the important potential connection between the confined and unconfined plasma regions in regulating L-H transition dynamics.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Synthesizing High-Capacity Oxyfluoride Conversion Anodes by Direct Fluorination of Molybdenum Dioxide (MoO 2 )

High-capacity metal oxide conversion anodes for lithium-ion batteries (LIBs) are primarily limited by their poor reversibility and cycling stability. In this study, a promising approach has been developed to improve the electrochemical performance of a MoO 2 anode by direct fluorination of the prelithiated MoO 2 . The fluorinated anode contains a mixture of crystalline MoO 2 and amorphous molybdenum oxyfluoride phases, as determined from a suite of characterization methods including X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy, and scanning transmission electron microscopy. Electrochemical measurements indicate that fluorination facilitates the conversion reaction kinetics, which leads to increased capacity, higher coulombic efficiency, and better cycling stability as compared to the nonfluorinated samples. Overall, these results suggest that fluorination after prelithiation not only favors formation of the oxyfluoride phase but also improves the lithium-ion diffusivity and reversibility of the conversion reaction, making it an attractive approach to address the problems of conversion electrodes. These findings provide a new route to design high-capacity negative electrodes for LIBs.

25 ENERGY STORAGE↗
DOE OSTI2021

Predicting and Synthesizing Interface Stabilized 2D Layers

The compound (Pb 2 MnSe 3 ) 0.6 VSe 2 was predicted to be kinetically stable based on density functional theory (DFT) calculations on an island of Pb 2 MnSe 3 between layers of VSe 2 . This approach provides a high degree of freedom by not forcing interlayer lattice match, making it ideal to investigate the likelihood of formation of new incommensurate layer misfit structures. The free space around the island is critical, as it allows atoms to diffuse and hence exploring the local energy landscape around the initial configuration. (Pb 2 MnSe 3 ) 0.6 VSe 2 was synthesized via a near diffusionless reaction from precursors where a repeating sequence of elemental layers matches the local composition and layer sequence of the predicted compound. The VSe 2 layer consists of a Se–V–Se trilayer with octahedral coordination of the V atoms. The Pb 2 MnSe 3 layer consists of three rock-salt-like planes, with a MnSe layer between the planes of PbSe. The center MnSe plane stabilizes the puckering of the outer PbSe layers. Electrical properties indicate that (Pb 2 Mn 1 Se 3 ) 0.6 VSe 2 undergoes a charge density wave transition at ~100 K and orders ferromagnetically at 35 K. Overall, the combination of theory and experiment enables a faster convergence to new heterostructures than either approach in isolation.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Understanding Instability in Formamidinium Lead Halide Perovskites: Kinetics of Transformative Reactions at Grain and Subgrain Boundaries

Transformative and reconstructive reactions impart significant structural changes at particle boundaries of hybrid perovskites, which influence environmental stability and optoelectronic properties of these materials. Here, we investigate the moisture-induced transformative reactions in formamidinium based perovskites FAPbX 3 (X=I, Br) and show that the ambient stability of these materials can be adjusted from a few hours to several months. For FAPbI 3 , roles of water vapor, particle size, and light illumination on the kinetic pathways of the cubic (a) transformation to the hexagonal (d) phase are analyzed by X-ray diffraction, optical microscopy, photoluminescence and solid-state NMR spectroscopy techniques. The grain and sub-grain boundaries exhibit different α→δ-FAPbI 3 phase transformation kinetics. Our study suggests that the dynamic transformation involves the local water-induced dissolution of the cubic phase occurring at the crystal surfaces followed by precipitation of the hexagonal phase. Insights into structures and dynamics of a kinetically trapped α-|δ-FAPbI 3 are obtained by 1 H, 2 H, and 207 Pb ssNMR spectroscopy.

36 MATERIALS SCIENCE↗
DOE OSTI2021

An Electrochemically Activated Nanofilm for Sustainable Mg Anode with Fast Charge Transfer Kinetics

Highly reversible Mg plating/stripping is key for rechargeable Mg batteries and has typically been successfully demonstrated using transient electrochemical techniques such as cyclic voltammetry measurements. Furthermore, little effort has been invested in studying the stability of the electrode/electrolyte interface over an extended time. We report here the development of an in situ generated surface film for Mg anodes based on electrodeposited bismuth (E_Bi). This film improves the interfacial stability of Mg in contact with the electrolyte, particularly over an extended time, and possesses fast charge-transfer kinetics (<30 Ω∙cm 2 ) and low non-time-sensitive interfacial film resistance (ca. 5 Ω∙cm 2 ) for active Mg species.

25 ENERGY STORAGE↗
DOE OSTI2020

Single Ru Atoms Stabilized by Hybrid Amorphous/Crystalline FeCoNi Layered Double Hydroxide for Ultraefficient Oxygen Evolution

Abstract In view of the sluggish kinetics suppressing the oxygen evolution reaction (OER), developing efficient and robust OER catalysts is urgent and essential for developing efficient energy conversion technologies. Herein, hybrid amorphous/crystalline FeCoNi layered double hydroxide (LDH)‐supported single Ru atoms (Ru SAs/AC‐FeCoNi) are developed for enabling a highly efficient electrocatalytic OER. The amorphous outer layer in Ru SAs/AC‐FeCoNi is composed of abundant defect sites and unsaturated coordination sites, which can serve as anchoring sites to stabilize single Ru atoms. The crystalline inner has a highly symmetric rigid structure, thereby strengthening the stability of support for a long‐lasting OER. The synergistic effects endow this hybrid catalyst with extremely low overpotential (205 mV at 10 mA cm −2 ). Density functional theory calculation indicates that single Ru atoms stabilized by hybrid amorphous/crystalline FeCoNi LDH facilitate the formation of Ru–O* (rate‐determining step), thus accelerating the OER process.

Hu, Yidong↗