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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

A Comprehensive Analysis of the Interphasial and Structural Evolution over Long–Term Cycling of Ultrahigh–Nickel Cathodes in Lithium–Ion Batteries

Ultrahigh-Ni layered oxides hold great promise as high-energy-density cathodes at an affordable cost for lithium-ion batteries, yet their practical application is greatly hampered by the poor cyclability. Herein, by employing LiNi 0.94 Co 0.06 O 2 as a model cathode in a full-cell configuration, the interphasial and structural evolution processes of ultrahigh-Ni layered oxides are systematically investigated over the course of their service life (1500 cycles). By applying advanced analytic techniques (e.g., Li-isotope labeling, region-of-interest method), the dynamic chemical evolution on the cathode surface is revealed with spatial resolution, and the correlation between lattice distortion and cathode surface reactivity is established. Benefiting from in situ X-ray diffraction (XRD) analysis, the ultrahigh-Ni layered oxide is demonstrated to undergo dual-phase reaction mechanisms with huge lattice variation, which leads to a decrease in crystallinity and secondary particle pulverization. Furthermore, the critical impact of cathode surface reaction on the graphite anode–electrolyte interphase (AEI) is revealed at nanometer scale, and a universal chemical/physical evolution process of the AEI is illustrated, for the first time. Finally, the practical viability of ultrahigh-Ni layered oxides is demonstrated through Al-doping strategy. Finally, this work presents a comprehensive understanding of the structural and interphasial degradation of ultrahigh-Ni layered oxide cathodes for developing high-energy-density lithium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Faceted NiO(111) nanosheets: morphological and catalytic evolution for the oxygen evolution reaction

The renaissance of the energy system through the use of green hydrogen by water electrolysis lies behind the development of abundant, active, and scalable catalysts for the oxygen evolution reaction (OER). A fundumental understanding of the surface properties for these materials is of vital importance in producing viable heterogenous catalysts. In this feature article, we summarize several years of collaborative work on a uniquely faceted NiO(111) nanosheet possessing hexagonal holes with a focus on understanding how the evolution of the catalyst surface and bulk composition effects OER performance. The importance of surface faceting, morphological evolution, and metal combination by different doping strategies are all analyzed and summarized to further improve the material's performance. Furthermore, microwave and supercritical synthesis processes are utilized to understand how varying wet-chemical techniques effect the formation of the NiO(111) nanosheet and activity of the material. We discuss our chosen strategies and the difficulties encountered with optimizing a catalyst surface for the OER.

08 HYDROGEN↗
DOE OSTI2019

The Evolution of SlyA/RovA Transcription Factors from Repressors to Countersilencers in Enterobacteriaceae

Gene duplication and subsequent evolutionary divergence have allowed conserved proteins to develop unique roles. The MarR family of transcription factors (TFs) has undergone extensive duplication and diversification in bacteria, where they act as environmentally responsive repressors of genes encoding efflux pumps that confer resistance to xenobiotics, including many antimicrobial agents. We have performed structural, functional, and genetic analyses of representative members of the SlyA/RovA lineage of MarR TFs, which retain some ancestral functions, including repression of their own expression and that of divergently transcribed multidrug efflux pumps, as well as allosteric inhibition by aromatic carboxylate compounds. However, SlyA and RovA have acquired the ability to countersilence horizontally acquired genes, which has greatly facilitated the evolution of Enterobacteriaceae by horizontal gene transfer. SlyA/RovA TFs in different species have independently evolved novel regulatory circuits to provide the enhanced levels of expression required for their new role. Moreover, in contrast to MarR, SlyA is not responsive to copper. These observations demonstrate the ability of TFs to acquire new functions as a result of evolutionary divergence of both cis -regulatory sequences and in trans interactions with modulatory ligands. IMPORTANCE Bacteria primarily evolve via horizontal gene transfer, acquiring new traits such as virulence and antibiotic resistance in single transfer events. However, newly acquired genes must be integrated into existing regulatory networks to allow appropriate expression in new hosts. This is accommodated in part by the opposing mechanisms of xenogeneic silencing and countersilencing. An understanding of these mechanisms is necessary to understand the relationship between gene regulation and bacterial evolution. Here we examine the functional evolution of an important lineage of countersilencers belonging to the ancient MarR family of classical transcriptional repressors. We show that although members of the SlyA lineage retain some ancestral features associated with the MarR family, their cis -regulatory sequences have evolved significantly to support their new function. Understanding the mechanistic requirements for countersilencing is critical to understanding the pathoadaptation of emerging pathogens and also has practical applications in synthetic biology.

Microbiology↗
DOE OSTI2019

Assessing the mechanisms governing the daytime evolution of marine stratocumulus using large‐eddy simulation

Large‐eddy simulation (LES) output for a case of thin stratocumulus off the coast of California is examined in a mixed‐layer analysis framework to identify the specific mechanisms responsible for governing the evolution of the cloud system. An equation for cloud‐base height tendency isolates the individual cloud‐modulating mechanisms that control the evolution of boundary‐layer liquid‐water static energy ( S l ) and total water mixing ratio ( q T ). With a suitable spin‐up procedure, the control simulation performs admirably compared with observed estimates of liquid water content, vertical velocity variance, and radiative fluxes sampled during an aircraft field campaign. Investigation of the cloud response to various environmental forcing scenarios was addressed through a suite of sensitivity simulations, including variations in subsidence velocity, surface fluxes, wind shear near the inversion, and radiative forcing. In the control simulation, rising cloud‐base tendencies are associated with entrainment warming/drying and short‐wave absorption, whereas lowering cloud‐base tendencies are driven by long‐wave cooling. Even in the presence of substantial afternoon solar heating, entrainment fluxes remained active. The thin cloud demonstrated unexpected resiliency, with mixed‐layer analysis indicating that, as the short‐wave flux decreases later in the afternoon, the relative contribution of long‐wave cooling often becomes large enough to offset entrainment warming/drying and result in a reversal of cloud‐base tendency. The evolution of cloud‐base tendency is found to be insensitive to the net radiative flux divergence for most of the simulations (liquid water path ranging from ~10–50 g/m 2 ). Error analysis in comparison with LES S l and q T budgets suggests that our method of entrainment flux calculation could be improved by a more complete understanding of entrainment‐layer physics.

McMichael, Lucas A.↗
DOE OSTI2023

Bottom-up evolution of perovskite clusters into high-activity rhodium nanoparticles toward alkaline hydrogen evolution

Self-reconstruction has been considered an efficient means to prepare efficient electrocatalysts in various energy transformation process for bond activation and breaking. However, developing nano-sized electrocatalysts through complete in-situ reconstruction with improved activity remains challenging. Herein, we report a bottom-up evolution route of electrochemically reducing Cs 3 Rh 2 I 9 halide-perovskite clusters on N-doped carbon to prepare ultrafine Rh nanoparticles (~2.2 nm) with large lattice spacings and grain boundaries. Various in-situ and ex-situ characterizations including electrochemical quartz crystal microbalance experiments elucidate the Cs and I extraction and Rh reduction during the electrochemical reduction. These Rh nanoparticles from Cs 3 Rh 2 I 9 clusters show significantly enhanced mass and area activity toward hydrogen evolution reaction in both alkaline and chlor-alkali electrolyte, superior to liquid-reduced Rh nanoparticles as well as bulk Cs 3 Rh 2 I 9 -derived Rh via top-down electro-reduction transformation. Theoretical calculations demonstrate water activation could be boosted on Cs 3 Rh 2 I 9 clusters-derived Rh nanoparticles enriched with multiply sites, thus smoothing alkaline hydrogen evolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Cloud System Evolution in the Trades (CSET): Following the Evolution of Boundary Layer Cloud Systems with the NSF–NCAR GV

The Cloud System Evolution in the Trades (CSET) study was designed to describe and explain the evolution of the boundary layer aerosol, cloud, and thermodynamic structures along trajectories within the North Pacific trade winds. The study centered on seven round trips of the National Science Foundation–National Center for Atmospheric Research (NSF–NCAR) Gulfstream V (GV) between Sacramento, California, and Kona, Hawaii, between 7 July and 9 August 2015. The CSET observing strategy was to sample aerosol, cloud, and boundary layer properties upwind from the transition zone over the North Pacific and to resample these areas two days later. Global Forecast System forecast trajectories were used to plan the outbound flight to Hawaii with updated forecast trajectories setting the return flight plan two days later. Two key elements of the CSET observing system were the newly developed High-Performance Instrumented Airborne Platform for Environmental Research (HIAPER) Cloud Radar (HCR) and the high-spectral-resolution lidar (HSRL). Together they provided unprecedented characterizations of aerosol, cloud, and precipitation structures that were combined with in situ measurements of aerosol, cloud, precipitation, and turbulence properties. The cloud systems sampled included solid stratocumulus infused with smoke from Canadian wildfires, mesoscale cloud–precipitation complexes, and patches of shallow cumuli in very clean environments. Ultraclean layers observed frequently near the top of the boundary layer were often associated with shallow, optically thin, layered veil clouds. In conclusion, the extensive aerosol, cloud, drizzle, and boundary layer sampling made over open areas of the northeast Pacific along 2-day trajectories during CSET will be an invaluable resource for modeling studies of boundary layer cloud system evolution and its governing physical processes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Evaluating the Lagrangian Evolution of Subtropical Low Clouds in GCMs Using Observations: Mean Evolution, Time Scales, and Responses to Predictors

In this work, a Lagrangian framework is developed to show the daily-scale time evolution of low clouds over the eastern subtropical oceans. An identical framework is applied to two general circulation models (GCMs): the CAM5 and UKMET and a set of satellite observations. This approach follows thousands of parcels as they advect downwind in the subtropical trade winds, comparing cloud evolution in time and space. This study tracks cloud cover, in-cloud liquid water path (CLWP), droplet concentration $N_d$, planetary boundary layer (PBL) depth, and rain rate as clouds transition from regions with predominately stratiform clouds to regions containing mostly trade cumulus. The two models generate fewer clouds with greater $N_d$ relative to observations. Models show stronger Lagrangian cloud cover decline and greater PBL deepening when compared with observations. In comparing frequency distributions of cloud variables over time, it is seen that models generate increasing frequencies of nearly clear conditions at the expense of overcast conditions, whereas observations show transitions from overcast to cloud amounts between 50% and 90%. Lagrangian decorrelation time scales ($\mathcal{e}$-folding time $\tau$) of cloud cover and CLWP are between 11 and 19 h for models and observations, although they are a bit shorter for models. A Lagrangian framework applied here resolves and compares the time evolution of cloud systems as they adjust to environmental perturbations in models and observations. Increasing subsidence in the overlying troposphere leads to declining cloud cover, CLWP, PBL depth, and rain rates in models and observations. Modeled cloud responses to other meteorological variables are less consistent with observations, suggesting a need for continuing mechanical improvements in GCMs.

58 GEOSCIENCES↗
NASA NTRS1989

Stochastic evolution of refractory interstellar dust during the chemical evolution of a two-phase interstellar medium

The evolution course of refractoary interstellar dust during the chemical evolution of a two-phase interstellar medium (ISM) is studied using a simple model of the chemical evolution of ISM. It is assumed that, in this medium, the stars are born in molecular clouds, but new nucleosynthesis products and stellar return are entered into a complementary diffuse medium; the well-mixed matter of each interstellar phase is repeatedly cycled stochastically through the complementary phase and back. The dust is studied on a particle-by-particle bases as it is sputtered by shock waves in the diffuse medium, accretes an amorphous mantle of gaseous refractory atoms while its local medium joins the molecular cloud medium, and encounters the possibility of astration within molecular clouds. Results are presented relevant to the size spectrum of accreted mantles, its age spectrum and the distinction among its several lifetimes, depletion factors of refractory atoms in the diffuse gas, and isotopic anomalies.

Liffman, Kurt↗
NASA NTRS1991

On the origin and early evolution of biological catalysis and other studies on chemical evolution

One of the lines of research in molecular evolution which we have developed for the past three years is related to the experimental and theoretical study of the origin and early evolution of biological catalysis. In an attempt to understand the nature of the first peptidic catalysts and coenzymes, we have achieved the non-enzymatic synthesis of the coenzymes ADPG, GDPG, and CDP-ethanolamine, under conditions considered to have been prevalent on the primitive Earth. We have also accomplished the prebiotic synthesis of histidine, as well as histidyl-histidine, and we have measured the enhancing effects of this catalytic dipeptide on the dephosphorylation of deoxyribonucleotide monophosphates, the hydrolysis of oligo A, and the oligomerization 2', 3' cAMP. We reviewed and further developed the hypothesis that RNA preceded double stranded DNA molecules as a reservoir of cellular genetic information. This led us to undertake the study of extant RNA polymerases in an attempt to discover vestigial sequences preserved from early Archean times. In addition, we continued our studies of on the chemical evolution of organic compounds in the solar system and beyond.

Oro, J.↗
DOE OSTI2021

Understanding the Electronic Structure Evolution of Epitaxial LaNi1-xFexO3 Thin Films for Water Oxidation

Rare earth nickelates including LaNiO3 are promising catalysts for water electrolysis to produce oxygen gas. Recent studies report that Fe substitution for Ni can significantly enhance the oxygen evolution reaction (OER) activity of LaNiO3. However, the role of Fe in increasing activity remains ambiguous, with potential origins both structural and electronic in nature. Here, by utilizing a series of epitaxial LaNi1-xFexO3 thin films synthesized by oxygen-assisted molecular beam epitaxy, we report that Fe substitution tunes the oxidation state of Ni in LaNi1-xFexO3 and a volcano-like OER trend is observed with x = 0.375 being the most active. Spectroscopy and ab initio modeling reveal that the high-valent Fe3+? B-site cationic species strongly increases the transition metal (TM) 3d bandwidth via Ni-O-Fe bridges and enhances the TM 3d-O 2p hybridization, boosting the OER activity. Furthermore, pH-dependent electrochemical measurements suggest that the OER on LaNi1-xFexO3 involves a lattice oxygen-mediated mechanism.

LaNiO3, Fe substitution, charge transfer, lattice ↗
DOE OSTI2021

Mesoscale-architecture-based crack evolution dictating cycling stability of advanced lithium ion batteries

The cracking phenomenon of Ni-rich NMC (LiNixMnyCo1-x-yO2, x = 0.6) secondary particles is frequently discovered and believed to be one of critical reasons deteriorating the long-term cycling stability of NMC cathode in lithium ion batteries (LIBs). However, the initiation and evolution of those cracks is still controversial due to the limited quantification especially by in situ monitoring, leading to the challenge of identifying an efficient approach to inhibit the formation of the fractures during repeated cycling. Herein, the irreversible, anisotropic cycling lattice and mesoscale expansion/shrinkage of nano-grain during the first cycle, as revealed by in situ X-ray diffraction (XRD) and in situ atomic force microscopy (AFM), have been quantified and confirmed to be the dominant driving forces of microcracks initiation at the grain boundaries. These microcracks preferentially nucleates at the core region with random oriented nano-grains in early stage. The further growth and aggregation of microcracks into macrocrack eventually results in microfracture propagation radially outward to the periphery region with more uniform nano-grain orientation. This mesoscale nano-grain architecture controlled cracking process highlight the importance of predictive synthesis of cathode materials with controllable multiscale crystalline architecture for high-performance LIBs.

25 ENERGY STORAGE↗
DOE OSTI2019

Electrocatalytic Hydrogen Evolution in Neutral pH Solutions: Dual-Phase Synergy

Electrolysis in neutral pH solutions (e.g., wastewater and seawater) presents a transformative way for environmentally friendly, cost-effective hydrogen production. However, one of the biggest challenges is the lack of active, robust hydrogen evolution reaction (HER) catalysts. Herein we present a catalyst with dual active sites of MoP2 and MoP which function synergistically to promote HER in neutral pH solutions. In our microbial electrolysis cell (MEC) which uses neutral pH wastewater as a feedstock, the new catalyst generates an average HER current density of ~157 A m-2Cathode-Surface-Area, higher than Pt/C (~145 A m-2Cathode-Surface-Area), ~5 times higher than the state-of-art platinum-group-metal (PGM)-free catalysts in MECs. The new catalyst also outperforms Pt/C in natural seawater with ~10% higher and more stable HER current density. The fundamental reason for the enhanced HER performance is identified to be the synergy between MoP2 and MoP phases, with MoP2 promoting H2O chemisorption/dissociation and MoP efficiently converting Hads to H2.

Xie, Xiaohong↗
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 OSTI2019

Controlling 3-D Morphology of Ni-Fe-Based Nanocatalysts for Oxygen Evolution Reaction

Controlling the 3-D morphology of nanocatalysts is one of the underexplored but important approaches for improving the sluggish kinetics of the oxygen evolution reaction (OER) in water electrolysis. This work reports a scalable, oil-based method based on thermal decomposition of organometallic complexes to yield highly uniform Ni–Fe-based nanocatalysts with a well-defined morphology (i.e. Ni–Fe core–shell, Ni/Fe alloy, and Fe–Ni core–shell). Transmission electron microscopy reveals their morphology and composition to be NiOx–FeOx/NiOx core-mixed shell, NiOx/FeOx alloy, and FeOx–NiOx core–shell. X-ray techniques resolve the electronic structures of the bulk and are supported by electron energy loss spectroscopy analysis of individual nanoparticles. These results suggest that the crystal structure of Ni is most likely to contain α-Ni(OH)2 and that the chemical environment of Fe is variable, depending on the morphology of the nanoparticle. The Ni diffusion from the amorphous Ni-based core to the iron oxide shell makes the NiOx–NiOx/FeOx core-mixed shell structure the most active and the most stable nanocatalyst, which outperforms the comparison NiOx/FeOx alloy nanoparticles expected to be active for the OER. This study suggests that the chemical environment of the mixed NiOx/FeOx alloy composition is important to achieve high electrocatalytic activity for the OER and that the 3-D morphology plays a key role in the optimization of the electrocatalytic activity and stability of the nanocatalyst for the OER.

Nanocatalysts↗
DOE OSTI2021

Functionalized Embedded Monometallic Nickel Catalysts for Enhanced Hydrogen Evolution: Performance and Stability

Viable anionic exchange membrane (AEM) electrolysis for H 2 production requires highly active hydrogen evolution reaction (HER) catalysts that are also robust and cost-effective. Traditionally juxtaposition of two transition metals with one being more oxophilic is necessary for easier access to water in the inner Helmholtz plane as a source of protons in the crucial Volmer step for enhanced HER activity. However, they are prone to passivation at anodic potentials or deactivation via the formation of sub-surface metal hydrides at high cathodic overpotentials. Here we report a method of enabling close juxtaposition of Ni-Ni-oxide surfaces by functionalizing Ni-based catalysts via the careful thermal treatment of carbon-supported Ni nano-particles chelated with a select organic chelating compound referred to as cupferron. This functionalization results in an embedded Ni surface with a clear graphitic coating engendering long-term stability for passivation and subsurface hydride formation. The stability and activity of the functionalized Ni catalyst are demonstrated in half-cell RDE and full-cell AEM membrane-based hydrogen pump experiments. In the case of the latter, the functionalized Ni outperforms carbon-supported Pt.

25 ENERGY STORAGE↗