Search NASA⌕ Search

SEARCH · Search NASA

Results for “Nudging”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
NASA NTRS2020

Comparison of Surface Fluxes Derived from CYGNSS and Simulated by WRF Model: An MJO Case Study

This study focuses on ocean surface fluxes, mainly the latent heat flux, and their impact on MJO propagation and associated precipitation structures over the Indian Ocean and Maritime Continent. The Coupled-Ocean-Atmosphere-Wave-Sediment Transport (COAWST) model is used to simulate two MJO events during the 2017-2018 season: the December 10 - January 20, 2017 case, which maintained its strong precipitation signal over the Maritime Continent, and the March 1 - 20, 2018 case, which was weaker and did not propagate through the Maritime Continent. Both simulated MJO events show positive biases in surface rainfall compared with GPM IMERG data. During the MJO suppressed phase, the simulations rain more often than the observations. During the active phase, the westward propagating precipitation structures are more organized and much stronger compared with the observations, sometimes forming westward propagating cyclones that weakened the eastward precipitation signals. Two aspects of the surface flux interactions are investigated: the impact of the domain mean surface fluxes, and the impact of storm scale circulations and their interactions with local surface fluxes. Both aspects affect water vapor budget, atmosphere instability and mean flow, through which convection initiation, organization, and propagation are influenced. Model sensitivity tests with different radiation, microphysics, PBL schemes and nudging schemes indicate that in the control simulations, higher SST and surface fluxes, especially during the suppressed period, are the main reason of rainfall overestimation compared with IMERG data. The strong westward propagating signals are caused by both increased atmosphere instability and reduced mean wind shear. Unfortunately, the small differences in mean SST and surface fluxes between different model sensitivity tests are all within the satellite observation error margin, and cannot be directly corroborated by observations. One of the advantages of CYGNSS satellites is that they observe ocean surface wind and heat fluxes underneath strong rainfall events such as the convective systems associated with MJO active phases. Currently we are comparing CYGNSS level 2 surface fluxes retrievals and the model simulations in order to better understand the second aspect of the MJO and surface fluxes interactions, and how this affects MJO strengths and propagations. The interactive atmosphere-ocean-wave model also provides cases that directly comparing satellite observables (the bistatic radar cross section) and the model simulations (through CYGNSS satellite simulator). These discrepancies are more prominent in coupled ocean simulations, mainly due to higher SST and enhanced surface fluxes.

Li, Xiaowen↗
NASA NTRS2020

Description and Evaluation of the Specified-Dynamics Experiment in the Chemistry-Climate Model Initiative

We provide an overview of the REF-C1SD specified-dynamics experiment that was conducted as part of phase 1 of the Chemistry-Climate Model Initiative (CCMI). The REF-C1SD experiment, which consisted of mainly nudged general circulation models (GCMs) constrained with (re)analysis fields, was designed to examine the influence of the large-scale circulation on past trends in atmospheric composition. The REF-C1SD simulations were produced across various model frameworks and are evaluated in terms of how well they represent different measures of the dynamical and transport circulations. In the troposphere there are large (~40 %) differences in the climatological mean distributions, seasonal cycle amplitude, and trends of the meridional and vertical winds. In the stratosphere there are similarly large (~50 %) differences in the magnitude, trends and seasonal cycle amplitude of the transformed Eulerian mean circulation and among various chemical and idealized tracers. At the same time, interannual variations in nearly all quantities are very well represented, compared to the underlying reanalyses. We show that the differences in magnitude, trends and seasonal cycle are not related to the use of different reanalysis products; rather, we show they are associated with how the simulations were implemented, by which we refer both to how the large-scale flow was prescribed and to biases in the underlying free-running models. In most cases these differences are shown to be as large or even larger than the differences exhibited by free-running simulations produced using the exact same models, which are also shown to be more dynamically consistent. Overall, our results suggest that care must be taken when using specified-dynamics simulations to examine the influence of large-scale dynamics on composition.

Clara Orbe↗
NASA NTRSDate not supplied

Impact of COVID-Global Shutdown on Earth's Radiation Budget

Climate is fueled by how much of the sun’s energy is absorbed by Earth. Changes in aerosol emissions have a direct impact how much solar energy is absorbed under clear-sky conditions, which occurs roughly one-third of the time globally. Aerosol emission changes can also indirectly influence clouds and further alter solar energy absorption. In this presentation, we examine the impact of the COVID-19 global shutdown on Earth’s radiation budget at global and regional scales and compare it with other changes that have had an influence on Earth's radiation budget during the past 20 years—including policy-related emission controls, wildfire events and changes in sea-ice extent in polar regions. We use a novel analysis technique together with data from NASA instruments on the Terra, Aqua and Aura satellites and reanalysis data from MERRA-2. We also compare results with state-of-the-art general circulation models that have been nudged to reanalysis data (winds, air temperature and surface 25 pressure) at all levels. Our preliminary results show that the largest COVID-19 impact occurs regionally over the East Asian Marginal Seas, just off the coast of China. We find a 30% reduction in aerosol optical depth according to the MODIS instrument, and an 8% reduction in reflected solar radiation according to the CERES radiation budget instrument. The climate model simulations show remarkable consistency with the observations and furthermore show no evidence of an indirect effect on cloud properties.

Norman G. Loeb↗
NASA NTRSDate not supplied

Evaluation of the GEOS-Chem UCX Stratosphere in the GEOS Composition Forecast System

The NASA GEOS Composition Forecast (GEOS-CF) system provides 3-dimensional atmospheric composition analyses and forecasts to the public in near-real time at the high spatial resolution of 25 km. While the main focus of this new product is on tropospheric air quality information, the GEOS-Chem chemistry model (v12) used in this system includes the UCX stratospheric chemistry mechanism. Here, we describe the GEOS-CF system and provide comparisons against remote-sensed observations for stratospheric composition, including measurements of HCl, ClO, NO2, and O3. The GEOS-CF nudges the stratospheric ozone towards the GEOS Forward Processing (GEOS FP) assimilated ozone product; as a result the stratospheric ozone analysis in theGEOS-CF agrees well with observations. Additionally, with the inclusion of the GEOS-Chem UCX stratospheric chemistry mechanism in GEOS-CF, 5-day forecasts, especially during the abnormal 2020 NH polar spring, capture the chemical and dynamical changes missed by the GEOS FP system, which tends towards climatology. The GEOS-CF is a new tool for the research community providing near-real time 3-dimensional gridded information on atmospheric composition throughout the troposphere and stratosphere.

Stratosphere↗
NASA NTRS2021

Land-Atmosphere Coupling at the U.S. Southern Great Plains: A Comparison on Local Convective Regimes Between ARM Observations, Reanalysis, and Climate Model Simulations

Using the 9-yr warm-season observations at the Atmospheric Radiation Measurement Southern Great Plains site, we assess the land-atmosphere (L-A) coupling in North American Regional Reanalysis (NARR) and two climate models: hindcasts with the Community Atmosphere Model version 5.1 by Cloud-Associated Parameterizations Testbed (CAM5-CAPT) and nudged runs with the Energy Exascale Earth System Model Atmosphere Model version 1 Regionally Refined Model (EAMv1-RRM). We focus on three local convective regimes and diagnose model behaviors using the Local Coupling metrics (Santanello et al. 2018). NARR agrees well with observations except a slightly warmer and drier surface with higher downwelling shortwave radiation and lower evaporative fraction. On clear-sky days, it shows warmer and drier early-morning conditions in both models with significant underestimates in surface evaporation by EAMv1-RRM. On the majority of the ARM-observed shallow cumulus days, there is no or little low-level clouds in either model. When captured in models, the simulated shallow cumulus shows much less cloud fraction and lower cloud bases than observed. On the days with late-afternoon deep convection, models tend to present a stable early-morning lower atmosphere more frequently than the observations, suggesting that the deep convection is triggered more often by elevated instabilities. Generally, CAM5-CAPT can reproduce the local L-A coupling processes to some extent due to the constrained early-morning conditions and large-scale winds. EAMv1-RRM exhibits large precipitation deficits and warm and dry biases towards mid-to-late summers, which may be an amplification through a positive L-A feedback among initial atmosphere and land states, convection triggering and large-scale circulations.

land-atmosphere↗
NASA NTRS1994

An Approximate Kalman Filter for Ocean Data Assimilation; An Example with an Idealized Gulf Stream Model

A practical method of data assimilation for use with large, nonlinear, ocean general circulation models is explored. A Kalman filter based on approximations of the state error covariance matrix is presented, employing a reduction of the effective model dimension, the error's asymptotic steady-state limit, and a time-invariant linearization of the dynamic model for the error integration. The approximations lead to dramatic computational savings in applying estimation theory to large complex systems. We examine the utility of the approximate filter in assimilating different measurement types using a twin experiment of an idealized Gulf Stream. A nonlinear primitive equation model of an unstable east-west jet is studied with a state dimension exceeding 170,000 elements. Assimilation of various pseudo measurements is examined, including velocity, density, and volume transport at localized arrays, and realistic distributions of satellite altimetry and acoustic tomography observations. Results are compared in terms of their effects on the accuracies of the estimation. The approximate filter is shown to outperform a previous study that used an empirical nudging scheme. The examples demonstrate that useful approximate estimation errors can be computed in a practical manner for general circulation models.

['Kalman↗
NASA NTRS2021

Impact of Regional Northern Hemisphere Mid-latitude Anthropogenic Sulfur Dioxide Emissions on Local and Remote Tropospheric Oxidants

The unintended consequences of reductions in regional anthropogenic sulfur dioxide (SO2) emissions implemented to protect human health are poorly understood. SO2 decreases began in the 1970s in the US and Europe and are expected to continue into the future, while recent emissions decreases in China are also projected to continue. In addition to the well-documented climate effects (warming) from reducing aerosols, tropospheric oxidation is impacted via aerosol modification of photolysis rates and radical sinks. Impacts on the hydroxyl radical and other trace constituents directly affect climate and air quality metrics such as surface ozone levels. We use the Geophysical Fluid Dynamics Laboratory Atmospheric Model version 3 nudged towards National Centers for Environmental Prediction (NCEP) reanalysis wind velocities to estimate the impact of SO2 emissions from the US, Europe, and China by differencing a control simulation with an otherwise identical simulation in which 2015 anthropogenic SO2 emissions are set to zero over one of the regions. Springtime sulfate aerosol changes occur both locally to the emission region and also throughout the Northern Hemispheric troposphere, including remote oceanic regions and the Arctic. Hydroperoxy (HO2) radicals are directly removed via heterogeneous chemistry on aerosol surfaces, including sulfate, in the model, and we find that sulfate aerosol produced by SO2 emissions from the three individual northern mid-latitude regions strongly reduces both HO2 and hydroxyl (OH) by up to 10 % year-round throughout most of the troposphere north of 30∘ N latitude. Regional SO2 emissions significantly increase nitrogen oxides (NOx) by about 5 %–8 % throughout most of the free troposphere in the Northern Hemisphere by increasing the NOx lifetime as the heterogeneous sink of HO2 on sulfate aerosol declines. Despite the NOx increases, tropospheric ozone decreases at northern mid-latitudes by 1 %–4 % zonally averaged and by up to 5 ppbv in summertime surface air over China, where the decreases in HO2 and OH suppress O3 production. Since 2015 anthropogenic SO2 emissions in China exceed those in the US or Europe, the oxidative response is greatest for the China perturbation simulation. Chemical effects of aerosols on oxidation (reactive uptake) dominate over radiative effects (photolysis rates), the latter of which are only statistically significant locally for the large perturbation over China. We find that the SO2 emissions decrease in China, which has yet to be fully realized, will have the largest impact on oxidants and related species in the Northern Hemisphere free troposphere compared to future decreases in Europe or the US. Our results bolster previous calls for a multipollutant strategy for air pollution mitigation to avoid the unintended consequence of aerosol removal leading to surface ozone increases that offset or mask surface ozone gains achieved by regulation of other pollutants, especially in countries where current usage of high-sulfur emitting fuels may be phased out in the future.

anthropogenic sulfur dioxide emissions↗
NASA NTRS2021

Cold Season Performance of the NU-WRF Regional Climate Model in the Great Lakes Region

As Earth’s largest collection of freshwater, the Laurentian Great Lakes have enormous ecological and socio-economic value. Their basin has become a regional hotspot of climatic and limnological change, potentially threatening its vital natural resources. Consequentially, there is a need to assess the current state of climate models regarding their performance across the Great Lakes region and develop the next generation of high-resolution regional climate models to address complex limnological processes and lake-atmosphere interactions. In response to this need, the current paper focuses on the generation and analysis of a 20-member ensemble of 3-km National Aeronautics and Space Administration (NASA)-Unified Weather Research and Forecasting (NU-WRF) simulations for the 2014-2015 cold season. The study aims to identify the model’s strengths and weaknesses; optimal configuration for the region; and the impacts of different physics parameterizations, coupling to a 1D lake model, time-variant lake-surface temperatures, and spectral nudging. Several key biases are identified in the cold-season simulations for the Great Lakes region, including an atmospheric cold bias that is amplified by coupling to a 1D lake model but diminished by applying the Community Atmosphere Model radiation scheme and Morrison microphysics scheme; an excess precipitation bias; anomalously early initiation of fall lake turnover and subsequent cold lake bias; excessive and overly persistent lake ice cover; and insufficient evaporation over Lakes Superior and Huron. The research team is currently addressing these key limitations by coupling NU-WRF to a 3D lake model in support of the next generation of regional climate models for the critical Great Lakes Basin.

Michael Notaro↗
NASA NTRS2022

NASA GEOS Composition Forecast Modeling System GEOS-CF v1.0: Stratospheric Composition

The NASA Goddard Earth Observing System (GEOS) Composition Forecast (GEOS-29CF) provides recent estimates and five-day forecasts of atmospheric composition to the public in near-real time. To do this, the GEOS Earth system model is coupled with the GEOS-Chem tropospheric-stratospheric unified chemistry extension (UCX) to represent composition from the surface to the top of the GEOS atmosphere (0.01 hPa). The GEOS-CF system is described, including updates made to the GEOS-Chem UCX mechanism within GEOS-CF for improved representation of stratospheric chemistry. Comparisons are made against balloon, lidar and satellite observations for stratospheric composition, including measurements of ozone (O3) and important nitrogen and chlorine species related to stratospheric O3recovery. The GEOS-CF nudges the stratospheric O3towards the GEOS Forward Processing (GEOS FP) assimilated O3product; as a result the stratospheric O3in the GEOS-CF historical estimate agrees well with observations. During abnormal dynamical and chemical environments such as the 2020 polar vortexes, the GEOS-CF O3forecasts are more realistic than GEOS FP O3forecasts because of the inclusion of the complex GEOS-Chem UCX stratospheric chemistry. Overall, the spatial patterns of the GEOS-CF simulated concentrations of stratospheric composition agree well with satellite observations. However, there are notable biases – such as low NOx and HNO3 in the polar regions and generally low HCl throughout the stratosphere – and future improvements to the chemistry mechanism and emissions are discussed. GEOS-CF is a new tool for the research community and instrument teams observing trace gases in the stratosphere and troposphere, providing near-real-time three-dimensional gridded information on atmospheric composition.

GEOS-CF↗
NASA NTRS2023

Sensitivity of the MAR Regional Climate Model Snowpack to the Parameterization of the Assimilation of Satellite-Derived Wet-Snow Masks on the Antarctic Peninsula

Both regional climate models (RCMs) and remote sensing (RS) data are essential tools in understanding the response of polar regions to climate change. RCMs can simulate how certain climate variables, such as surface melt, runoff and snowfall, are likely to change in response to different climate scenarios but are subject to biases and errors. RS data can assist in reducing and quantifying model uncertainties by providing indirect observations of the modeled variables on the present climate. In this work, we improve on an existing scheme to assimilate RS wet snow occurrence data with the “Modèle Atmosphérique Régional” (MAR) RCM and investigate the sensitivity of the RCM to the parameters of the scheme. The assimilation is performed by nudging the MAR snowpack temperature to match the presence of liquid water observed by satellites. The sensitivity of the assimilation method is tested by modifying parameters such as the depth to which the MAR snowpack is warmed or cooled, the quantity of water required to qualify a MAR pixel as “wet” (0.1 % or 0.2 % of the snowpack mass being water), and assimilating different RS datasets. Data assimilation is carried out on the Antarctic Peninsula for the 2019–2021 period. The results show an increase in meltwater production (+66.7 % on average, or +95 Gt), along with a small decrease in surface mass balance (SMB) (−4.5 % on average, or −20 Gt) for the 2019–2020 melt season after assimilation. The model is sensitive to the tested parameters, albeit with varying orders of magnitude. The prescribed warming depth has a larger impact on the resulting surface melt production than the liquid water content (LWC) threshold due to strong refreezing occurring within the top layers of the snowpack. The values tested for the LWC threshold are lower than the LWC for typical melt days (approximately 1.2 %) and impact results mainly at the beginning and end of the melting period. The assimilation method will allow for the estimation of uncertainty in MAR meltwater production and will enable the identification of potential issues in modeling near-surface snowpack processes, paving the way for more accurate simulations of snow processes in model projections.

regional climate models↗
NASA NTRSDate not supplied

A Look at the Truths and Misconceptions of the Variational Quantum Eigensolver and the Implications of Overparameterization

In this work, we investigate loss landscapes of the variational quantum eigensolver (VQE) by quantifying the number of local minima through empirical analyses. We focus on minimal models in chemistry and physics so that we can do a complete analysis using more computationally expensive tools. We employ Hessian eigenvalue calculations and the nudged elastic band algorithm to characterize these landscapes. Our results expand upon the existing literature by highlighting the optimization challenges faced by VQE. We find that, as the number of parameters in our ansatz increases, the number of basins increases while the corresponding loss function values converge toward the global minimum value. This observation implies that overparameterization may lead to an ``effective convexity'' in VQE loss landscapes, a phenomenon supported by theoretical and numerical work in classical machine learning.

quantum computing↗
NASA NTRSDate not supplied

Exploring the Use of a Ground-Based Laser System to Deorbit Small Orbital Debris

In March 2023, NASA Office of Technology, Policy, and Strategy (OTPS) released its Cost and Benefit Analysis of Orbital Debris Remediation report. This analysis found that the two most efficient methods for remediating orbital debris were the removal of small (1-10 cm) debris and nudging large debris away from predicted collisions; both methods could be performed by high-energy laser systems. To further explore the concept, OTPS has been assessing a reference mission using ground-based, pulsed lasers to detect, engage, and rapidly deorbit 1- to 10-cm debris that would otherwise threaten the safety of the International Space Station and future crewed platforms in low Earth orbit. In March of 2024, OTPS convened a technical interchange meeting (TIM) of experts in detection and tracking of debris, high-energy glass and excimer lasers, laser-matter interactions, atmospheric propagation, and adaptive optics. The TIM spanned two days, covering the unclassified state of the art, uncertainties, and technical challenges for the entire concept of operations of the reference mission. In this presentation, we will summarize the reference mission analyzed, key findings from the TIM, and solicit the feedback from this community to further define “what is good enough” for debris remediation.

orbital debris↗
NASA NTRSDate not supplied

Dynamic Adjustment of Model Parameters Using Assimilated Boundary Layer Height

The NASA Global Modeling and Assimilation Office is exploring the assimilation of boundary layer height (PBLH) derived from a variety of observations, including radiosondes, GNSS-RO, space- and ground-based lidar, and radar wind profilers. Previous work using the Goddard Earth Observing System (GEOS) has shown that within the lower troposphere, the representation of thermodynamic structure is strongly affected by model parameterizations. In assimilation experiments, parameterizations can compensate for analysis thermodynamic increments and reduce the observation information carried forward in time. To mitigate this effect, the present study explores a dynamic parameter adjustment based on the PBLH analysis field. The PBLH analysis increment is used to adjust model parameters that influence the depth of parameterized boundary layer mixing in both stable and convective regimes. Replay (nudging) experiments and cycled data assimilation experiments are used to evaluate the approach. The parameter adjustment is shown to reduce model compensation of the analysis thermodynamic tendencies and bring model parameterized mixing depths into closer agreement with observed PBLH.

Nathan Arnold↗
NASA NTRS2024

Envisioning an Optimal Network of Space-Based Lasers for Orbital Debris Remediation

The rapid increase in resident space objects, including satellites and orbital debris, poses a significant threat to the safety and sustainability of space missions. This paper explores orbital debris remediation using a network of collaborative space-based lasers, leveraging laser ablation for momentum transfer on debris. A novel delta-v vector analysis framework quantifies the e↵ects of multiple simultaneous laser-to-debris (L2D) engagements by using vector composition of the imparted delta-v vectors. The paper introduces the Concurrent LocationScheduling Problem (CLSP), which optimizes the placement of laser platforms and the scheduling of L2D engagements to maximize debris remediation capacity. Due to the computational complexity of the CLSP, it is decomposed into two sequential subproblems: (1) optimal laser platform locations are determined using the Maximal Covering Location Problem, and (2) a novel integer linear programming-based approach schedules L2D engagements within the network configuration to maximize remediation capacity. Computational experiments are conducted to evaluate the proposed framework’s e↵ectiveness under various mission scenarios, demonstrating key network functions such as collaborative nudging, deorbiting, and just-in-time collision avoidance. A sensitivity analysis further examines how varying the number and distribution of laser platforms a↵ects debris remediation capacity, providing insights into optimizing the performance of space-based laser networks.

David O Williams Rogers↗
DOE OSTI2020

STRUCTURE AND PROPERTIES STUDY ON ENERGY MATERIALS: THERMOELECTRIC MATERIAL TETRAHEDRITE AND LITHIUM ION CONDUCTOR

Development of efficient energy materials is critical in order to ease the energy demand and reduce our dependence of fossil fuel. Thermoelectric materials are promising due to their capability of generating electrical power by recovering waste heat. The performance of thermoelectric materials is quantified by a dimensionless figure of merit zT, which depends on their properties such as electrical conductivity, Seebeck coefficient and thermal conductivity. Tetrahedrites, a copper antimony sulfosalt mineral, typified by Cu 12-x MxSb 4 S 13 , where M is a transition metal element such as Ni, Zn, Fe or Mn, have great potential for thermoelectric application due to their relatively high zT (close to 1 at 700 K), earth-abundance, environmental friendliness, favorable electrical properties, and most importantly intrinsic low lattice thermal conductivity (less than 1 W m -1 K -1 ) in wide temperature. In addition to energy recovery, reliable energy storage devices are also emerging to relieve the energy demand and improve the efficiency of consuming energy resources. Lithium-ion batteries are known to be reliable and successful electrochemical energy storage devices and appliable in various aspects, including laptops, smartphones and electrical vehicles. Lithium phosphorous oxynitride (LiPON) are widely used as thin-film solid-state electrolytes in Li-ion battery, which is the only demonstrated solid-state electrolyte that is quite stable in direct contact with Li metal at potentials from 0-5 V. However, the structure of LiPON, the effects of N doping, and the origin of its good electrochemical stability remains inconclusive. In this thesis, reliable modeling techniques accompanied with experimental tools, are applied to study the thermoelectric material tetrahedrite and the ionic conductor LiPON, in order to study their structural and dynamical properties. Accurate and efficient density-functional theory (DFT) and density-functional tight-binding (DFTB) methods, combined with molecular dynamics (MD) simulations are utilized in order to investigate the structures and properties of these energy materials. The incoherent and coherent atomic dynamics study of tetrahedrite Cu 10.5 NiZn 0.5 Sb 4 S 13 provides the origin of softening upon cooling by investigate the motion of Cu12e at different temperatures. The dynamic structure factors in the longitudinal and transverse direction will also be discussed. The Cu movement of Cu-rich tetrahedrite Cu 14 Sb 4 S 13 is revealed by Cu self-diffusivity, nuclear density map and “nudged elastic band” (NEB). Moreover, we investigate the effect of simulation cell size and basis sets on the DFT-based MD simulation results using tetrahedrite Cu1 0 Zn 2 Sb 4 S 13 thermoelectric as a model material, showing the advantage of larger cell by accessing smaller Q range. In addition, the low-temperature structural properties of Cu 12 Sb 4 S 13 is measured by neutron diffraction, which indicates that no cubic to tetragonal transition occurs at metal-semiconductor transition (MST) temperature. Thermoelectric properties such as Seebeck coefficient, electrical resistivity and electrical thermal conductivity will also be investigated. DFTB method is implemented to study the structure and transport properties of Li 3 PO 4 and LiPON, while the exploration of N doping effect is included. Lastly, the LiPON/Li interphase will be revealed in order to study the origin of electrochemical stability.

Li, Junchao↗
DOE OSTI2020

STRUCTURE AND PROPERTIES STUDY ON ENERGY MATERIALS: THERMOELECTRIC MATERIAL TETRAHEDRITE AND LITHIUM ION CONDUCTOR LiPON

Development of efficient energy materials is critical in order to ease the energy demand and reduce our dependence of fossil fuel. Thermoelectric materials are promising due to their capability of generating electrical power by recovering waste heat. The performance of thermoelectric materials is quantified by a dimensionless figure of merit zT, which depends on their properties such as electrical conductivity, Seebeck coefficient and thermal conductivity. Tetrahedrites, a copper antimony sulfosalt mineral, typified by Cu12-xMxSb4S13, where M is a transition metal element such as Ni, Zn, Fe or Mn, have great potential for thermoelectric application due to their relatively high zT (close to 1 at 700 K), earth-abundance, environmental friendliness, favorable electrical properties, and most importantly intrinsic low lattice thermal conductivity (less than 1 W m-1 K-1) in wide temperature. In addition to energy recovery, reliable energy storage devices are also emerging to relieve the energy demand and improve the efficiency of consuming energy resources. Lithium-ion batteries are known to be reliable and successful electrochemical energy storage devices and appliable in various aspects, including laptops, smartphones and electrical vehicles. Lithium phosphorous oxynitride (LiPON) are widely used as thin-film solid-state electrolytes in Li-ion battery, which is the only demonstrated solid-state electrolyte that is quite stable in direct contact with Li metal at potentials from 0-5 V. However, the structure of LiPON, the effects of N doping, and the origin of its good electrochemical stability remains inconclusive.In this thesis, reliable modeling techniques accompanied with experimental tools, are applied to study the thermoelectric material tetrahedrite and the ionic conductor LiPON, in order to study their structural and dynamical properties. Accurate and efficient density-functional theory (DFT) and density-functional tight-binding (DFTB) methods, combined with molecular dynamics (MD) simulations are utilized in order to investigate the structures and properties of these energy materials. The incoherent and coherent atomic dynamics study of tetrahedrite Cu10.5NiZn0.5Sb4S13 provides the origin of softening upon cooling by investigate the motion of Cu12e at different temperatures. The dynamic structure factors in the longitudinal and transverse direction will also be discussed. The Cu movement of Cu-rich tetrahedrite Cu14Sb4S13 is revealed by Cu self-diffusivity, nuclear density map and "nudged elastic band" (NEB). Moreover, we investigate the effect of simulation cell size and basis sets on the DFT-based MD simulation results using tetrahedrite Cu10Zn2Sb4S13 thermoelectric as a model material, showing the advantage of larger cell by accessing smaller Q range. In addition, the low-temperature structural properties of Cu12Sb4S13 is measured by neutron diffraction, which indicates that no cubic to tetragonal transition occurs at metal-semiconductor transition (MST) temperature. Thermoelectric properties such as Seebeck coefficient, electrical resistivity and electrical thermal conductivity will also be investigated. DFTB method is implemented to study the structure and transport properties of Li3PO4 and LiPON, while the exploration of N doping effect is included. Lastly, the LiPON/Li interphase will be revealed in order to study the origin of electrochemical stability

25 ENERGY STORAGE↗
DOE OSTI2023

Assessing the Role of Interfacial and Metal Sites in Pt/TiO2-Catalyzed Acetic Acid Hydrodeoxygenation

Thermochemical conversion of biomass to produce drop-in quality biofuels typically involves hydrodeoxygenation (HDO) steps following catalytic fast pyrolysis (CFP) to remove excess oxygen and create a more-stable bio-oil product. HDO reactions are performed by co-feeding the CFP vapor-phase product and H2 gas over a bi-functional catalyst. Noble-metal catalysts supported on reducible metal oxides (e.g., Pt/TiO2) are active and selective toward these HDO reactions. Griffin and co-workers showed that Pt/TiO2 catalysts promote the desired deoxygenation steps for m-cresol HDO while mitigating undesired C-C bond-breaking steps that reduce the overall value/energy density of the biofuel. Such model-compound studies to inform the design of improved catalysts for HDO chemistry are necessary to improve the overall process economics/efficiencies for biofuels production. One important class of bio-derived compounds that has not been studied extensively with respect to HDO chemistry, particularly at the atomic level, is carboxylic acids. Past experimental work indicates that Pt/C and Pt/TiO2 catalysts are selective toward C-C and C-O bond-dissociation products for acetic acid HDO, respectively. To understand the role of Pt/TiO2 active sites in this observed change in selectivity and guide catalyst development, the work in this presentation focuses on modeling the role of Pt-metal and Pt-TiO2-interfacial sites in promoting key C-C bond-breaking, C-O bond-breaking, and (de)hydrogenation steps in acetic acid HDO. Density functional theory (DFT) calculations were performed using the Vienna Ab initio Simulation Package (VASP). The exchange-correlation functional was approximated by the Perdew-Burke-Ernzerhof functional. Dispersion interactions were captured using the D3 method. Projector augmented-wave potentials described electron-ion interactions, and electron wavefunctions were expanded via a planewave basis with an energy cutoff of 500 eV. Activation barriers were calculated using the climbing image nudged elastic band method. Results and Discussion: To discern the role of Pt-metal and Pt-TiO2 interface sites in promoting acetic acid HDO chemistry, Pt(111) slab and anatase TiO2(101)-supported Pt-nanowire (PtNW/OH-TiO2) surface models were constructed, respectively. Because H2 is co-fed in HDO reactions, the anatase support was terminated with OH groups. Interfacial vacancies have been shown to facilitate Ru/TiO2-catalyzed phenol HDO; thus, an interfacial model with an OH vacancy was also considered (PtNW/OHv-TiO2). Pt-TiO2-interface sites stabilize adsorption of all studied acetic acid HDO surface intermediates relative to terrace Pt-metal sites, particularly when an interfacial-OH vacancy is present. Oxygenated species prefer to bind at the OH vacancy through the O atom, suggesting a preference for C-O over C-C bond cleavage at these sites. This hypothesis is supported by net-negative and net-positive average shifts in the reaction energy and activation energy barriers for C-O and C-C bond-breaking steps, respectively, at Pt-TiO2-interface sites relative to Pt-metal sites. Using the calculated energetics, the predicted minimum-energy pathway was determined for each surface. Pt(111) is predicted to follow decarboxylation, producing undesired methane and carbon dioxide. Conversely, PtNW/OH-TiO2 and PtNW/OHv-TiO2 are both predicted to produce desired acetaldehyde and ethane. The interfacial vacancy may also play a key role in facilitating the first C-O bond-breaking step in acetic acid HDO, lowering the barrier by 0.6 eV relative to the defect-free interface model. These results demonstrate the critical role of the Pt-TiO2 interface in the shift in acetic acid HDO selectivity experimentally observed on Pt/C and Pt/TiO2 catalysts. The results herein demonstrate the important role of the Pt-TiO2 interface and interfacial oxygen vacancies in improving the carbon efficiency for HDO reactions in CFP upgrading.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗