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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 73 records · Page 4

Exploring Transport Behavior in Hybrid Perovskites Solar Cells via Machine Learning Analysis of Environmental-Dependent Impedance Spectroscopy

Hybrid organic–inorganic perovskites are one of the promising candidates for the next-generation semiconductors due to their superlative optoelectronic properties. However, one of the limiting factors for potential applications is their chemical and structural instability in different environments. Herein, the stability of (FAPbI3)0.85(MAPbBr3)0.15 perovskite solar cell is explored in different atmospheres using impedance spectroscopy. An equivalent circuit model and distribution of relaxation times (DRTs) are used to effectively analyze impedance spectra. DRT is further analyzed via machine learning workflow based on the non-negative matrix factorization of reconstructed relaxation time spectra. This exploration provides the interplay of charge transport dynamics and recombination processes under environment stimuli and illumination. The results reveal that in the dark, oxygen atmosphere induces an increased hole concentration with less ionic character while ionic motion is dominant under ambient air. Under 1 Sun illumination, the environment-dependent impedance responses show a more striking effect compared with dark conditions. In this case, the increased transport resistance observed under oxygen atmosphere in equivalent circuit analysis arises due to interruption of photogenerated hole carriers. The results not only shed light on elucidating transport mechanisms of perovskite solar cells in different environments but also offer an effective interpretation of impedance responses.

36 MATERIALS SCIENCE↗

Time-Dependent Corrosion Behavior of Aluminum Using Advanced Electrochemical and Characterization Techniques

The time-dependent corrosion behavior of pure aluminum (Al) in a chloride-containing environment was investigated using various electrochemical and characterization techniques for up to 336 h. Transmission electron microscopic and secondary ion mass spectroscopic analysis revealed the continuous dissolution of the surface film over the immersion time. In the meantime, the increasing passive oxide thickness resulted in the surface film resistance enhancement over the immersion time, as indicated by the electrochemical impedance spectroscopic analysis. The electrochemical noise measurements showed an increase in the corrosion kinetics with immersion time until 60 h because of the accelerated localized corrosion in the early stage of immersion. However, an inhibition in corrosion kinetics occurred after longer immersion times due to corrosion product deposition inside the pit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of V Content on Corrosion Behavior of Al-V Alloys Produced by Mechanical Alloying and Subsequent Spark Plasma Sintering

Al-V alloys produced via high-energy ball milling have been reported to show simultaneous improvement of corrosion resistance and mechanical properties compared to traditional Al alloys. In these alloys, V content plays a crucial role in increasing or decreasing the corrosion resistance. Therefore, the effect of V and microstructure on corrosion of high-energy ball milled and subsequently spark plasma sintered Al-xV alloys (x = 2, 5, 10 at%) has been studied. Cyclic potentiodynamic polarization tests and electrochemical impedance spectroscopic analysis revealed the increment of V content up to 5 at% enhanced the corrosion resistance of the alloy. However, highly heterogeneous microstructure in Al-10 at%V resulted in significant localized corrosion over the immersion time. The electrochemical impedance spectroscopy studies over 14 days of immersion revealed underlying corrosion mechanisms.

36 MATERIALS SCIENCE↗

Rheoencephalographic (REG) Assessment of Head and Neck Cooling for use with Multiple Sclerosis Patients

We have prepared a computer program (RHEOSYS:RHEOencephalographic impedance trace scanning SyStem) that can be used to automate the analysis of segmental impedance blood flow waveforms. This program was developed to assist in the post test analysis of recorded impedance traces from multiple segments of the body. It incorporates many of the blood flow, segmental volume, and vascular state indices reported in the world literature. As it is currently programmed, seven points are selected from each blood flow pulse and associated ECG waveforrn: 1. peak of the first ECG QRS complex, 2. start of systolic slope on the blood flow trace, 3. maximum amplitude of the impedance pulse, 4. position of the dicrotic notch, 5. maximum amplitude of the postdicrotic segment, 6. peak of the second ECG QRS complex, and 7. start of the next blood flow pulse. These points we used to calculate various geometric, area, and time-related values associated with the impedance pulse morphology. RHEOSYS then calculates a series of 34 impedance and cardiac cycle parameters which include pulse amplitudes; areas; pulse propagation times; cardiac cycle times; and various measures of arterial and various tone, contractility, and pulse volume. We used this program to calculate the scalp and intracranial blood flow responses to head and neck cooling as it may be applied to lower the body temperatures of multiple sclerosis patients. Twelve women and twelve men were tested using a commercially available head and neck cooling system operated at its maximum cooling capacity for a period of 30 minutes. Head and neck cooling produced a transient change in scalp blood flow and a significant, (P<0.05) decrease of approx. 30% in intracranial blood flow. Results of this experiment will illustrate how REG and RHEOSYS can be used in biomedical applications.

Montogomery, Leslie D.↗

Tracking the evolution of processes occurring in silicon anodes in lithium ion batteries by 3D visualization of relaxation times

An unconventional electroanalytical method has been used for tracking processes in silicon anodes in lithium ion batteries: a 3D visualization of relaxation times. Impedance data of the electrodes were collected at different potentials and different cycles during cyclic voltammetry, and were treated by means of the Distribution of Relaxation Times (DRT) method. A 3D visualization of the results allowed to identify the formation of a solid electrolyte interphase on the anode, composed of two layers with different relaxation times. Such findings are not possible by conventional analysis of impedance data by modeling with equivalent circuits, nor by simple DRT alone. Additionally, it was possible to observe that the characteristic relaxation time of the lithiation of the Si anode becomes smaller upon cycling, indicating that the material experiences structural transformations that allow it to lithiate faster. The result is relevant to motivate the use of micron-sized particles in the anode.

25 ENERGY STORAGE↗

Generalized wave envelope analysis of sound propagation in ducts with stepped noise source profiles and variable axial impedance

A finite difference formulation is presented for sound propagation in a rectangular two-dimensional duct without steady flow. Before the difference equations are formulated, the governing Helmholtz equation is first transformed to a form whose solution tends not to oscillate along the length of the duct. This transformation reduces the required number of grid points by an order of magnitude. Example solutions indicate that stepped noise source profiles have much higher attenuation than plane waves in a uniform impedance liner. Also, multiple stepped impedance liners are shown to have higher attenuation than uniform ducts if the impedances are chosen properly. For optimum noise reduction with axial variations in impedance, the numerical analysis indicates that for a plane wave input the resistance should be near zero at the entrance of a suppressor duct, while the reactance should be near the optimum value associated with the least-attenuated mode in a uniform duct.

Baumeister, K. J.↗

Evaluating Pressure‐dependent Discharge Behavior of Foil Versus In situ Plated Lithium Metal Anodes in Solid‐State Batteries

Abstract Anode‐free manufacturing of solid‐state batteries (SSBs) shows promise to maximize energy density by eliminating excess lithium (Li) and simplifying battery production. However, high reversibility during discharge (stripping of Li) is necessary for long‐lifetime SSBs with a limited Li reservoir. Further, the plastic flow of Li changes depending on the Li thickness, leading to possible differences in discharge performance under stack pressure. This work investigates the pressure‐dependent discharge performance of anode‐free manufactured SSBs with in situ plated Li and compares the performance to that of conventional thick Li foil cells. Distinct stripping behavior is observed at low pressures (0–1 MPa), where Li diffusivity and initial interfacial contact may control accessible capacity, compared to high pressures (3–10 MPa) where mechanical deformation of Li likely governs stripping behavior. Analysis of impedance spectra collected during stripping shows that additional stack pressure delays the formation of deep, as opposed to lateral, voids in the Li anode. These results provide insights to guide the transition from thick Li foil anodes to anode‐free manufactured SSBs.

Haslam, Catherine G.↗

Electrocatalytic Oxidative Coupling of Methane on NiFe Exsolved Perovskite Anode: Effect of Water

Oxidative coupling of methane (OCM) can be performed electrocatalytically by utilizing solid oxide cells, which provide a readily controlled oxygen supply through dense electrolytes. La 0.7 Sr 0.2 Ni 0.2 Fe 0.8 O 3 (LSNF) perovskite is an effective anode for OCM. Its surface characteristics and electrocatalytic activity can be improved by reduction and the resultant exsolution of bimetallic NiFe nanoparticles from its bulk. X-ray diffraction (XRD) and environmental transmission electron microscopy proved that the evolution of hetero-phases under reducing environment resulted in bimetallic NiFe nanoparticles being formed on the surface. Further, a 36 % improvement in C 2+ hydrocarbon production rate was achieved due to the reduction of LSNF with the exsolved NiFe nanoparticles. Co-feeding of H 2 O enhanced selective conversion of CH 4 resulting in the production rate of C 2+ hydrocarbons being increased by 56 %. Analysis of impedance spectra and in-situ DRIFTS under a CH 4 +H 2 O atmosphere provided an understanding for the enhancement on the electrocatalytic OCM.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exploring the Role of Humidity, Temperature, and Mixed Ionic and Electronic Conductivity on SOFC Anode Electrocatalysis

Infiltration of nanoscale electrocatalysts into Ni/yttria-stabilized zirconia (Ni-YSZ) cermets has been shown to improve the electrochemical performance of solid oxide fuel cell (SOFC) anodes. While infiltrated electrodes in SOFCs result in improved cell performance, long-term operation leads to coarsening of the infiltrated nanoparticles and negates the short-term performance improvements. This study explores the roles of humidity, temperature, and number of cycles of nanocatalyst infiltration in improving mixed conduction within the Ni-YSZ electrode. Two mixed conduction phases were studied: Gd 0.1 Ce 0.9 O 2-δ (GDC) as an infiltrant into Ni-YSZ electrodes, and Ni/transition metal doped-YSZ electrodes infiltrated with Ni. Analysis of impedance data from these cells shows improved electrochemical performance in infiltrated cells with mixed conduction compared with infiltrated cells containing purely ionic and electronic conducting phases. Improved anode performance is attributed to the availability of electronic pathways through predominantly ionic-conducting phases to connect distant Ni nanoparticles and/or Ni grains.

25 ENERGY STORAGE↗

Multiphysics modeling of SOFC performance degradation caused by interface delamination and active layer cracking

In solid oxide device operation, delamination and cracking cause more catastrophic damage to cell life than other degradation mechanisms, leading to more rapid cell failure. The electrochemical performance degradation caused by electrode/electrolyte interface delamination and active layer cracking were investigated through in-house developed three-dimensional multiphysics simulations. Here the multiphysics simulations, fully calibrated against experimental datasets for button cells in a previous study, were extended to quantitatively investigate the effects of electrode/electrolyte interface delamination and active layer cracking. The simulated polarization curves and impedance behavior with various levels of delamination and cracking provided insights of the performance degradation. Furthermore, the local current distributions within the cell were analyzed for three different operating modes: constant voltage, constant current, and constant power. Finally, a practical strategy was proposed to mitigate the performance degradation in the realistic cell operations, extending overall cell lifetime.

08 HYDROGEN↗

Surface enhanced performance of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ cathodes by infiltration Pr-Ni-Mn-O progress

Herein the present study reports the enhancement of electrochemical oxygen reduction activity of porous La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3–δ (LSCF) cathodes by coating a thin film of Pr-Ni-Mn oxide (PNM5) using a multi-step infiltration process. XRD examination reveals that PNM5 mainly contains a multiphase mixture of Pr 6 O 11 , PrNiO 3 , MnO and NiO. SEM morphology shows a thin PNM5 film and small particles are formed on the surface of LSCF backbone particles. Impedance spectrum analysis indicates that PNM5 infiltrated LSCF exhibits dramatically reduced polarization resistance (R p ), reaching R p of 0.244 Ω cm 2 at 973 K, which is one-half of the baseline LSCF cathode. The activation energy of LSCF cathodes infiltrated with PNM5 is 1.45 eV, slightly lower than the baseline LSCF cathode (1.77 eV). Distribution of relaxation time (DRT) function analysis shows PNM5 infiltration layer significantly promotes the oxygen reduction reaction (ORR) of cathode surface. With the increase in firing temperature, the total resistance increases and R p changes from ion transport to oxygen reduction reaction. Degradation rate of the PNM5-infiltrated LSCF is also lower, 0.02168% vs 0.07093% for the baseline LSCF over a 200-h period. A single cell testing indicated that the peak power density of the PNM5-infiltrated cell was increased by 140.66%. Overall, PNM5 could be a potential catalyst for boosting the performance of a commercial LSCF cathode for solid oxide fuel cells (SOFC).

36 MATERIALS SCIENCE↗

Photoelectrochemical and Photovoltaic Performance of As-deposited Ink-based CuInS 2 Heterojunction Thin Film

In this report, we demonstrate low-temperature ink-based fabrication of CuInS 2 -based photoelectrodes for hydrogen production capable of producing photocurrent densities as high as 8.8mA.cm -2 . In this process, molecular ink made of metal chlorides and thiourea dissolved in methanol was spin coated onto Mo-coated soda lime glass substrates. Samples were then placed on a hot plate (sample surface temperature: 250°C) to induce CuInS 2 formation and remove the solvent and by-products. No further processing, such as high temperature sulfurization, was performed. Further, the CuInS 2 films were then integrated as photocathode for hydrogen evolution by photoelectrodeposition of Pt nanoparticles. Photocurrent density of 0.4mA.cm -2 at 0V vs. RHE was detected from such electrodes. However, samples coated with CdS/ZnO/ITO overlayers forming heterojunction prior to Pt deposition exhibited significant improvement of the photocurrent density, reaching 8.8mA.cm -2 at 0V vs. RHE, highlighting the improved charge transfer by the p-n junction formed at the CuInS 2 /CdS interface. The charge transfer resistance of the CuInS 2 /CdS/ZnO/ITO-Pt photoelectrode was almost 5 times lower than that of the CuInS 2 -Pt photoelectrode as revealed by electrochemical impedance spectroscopy analysis. In addition, the onset potential was shifted by ca. 0.45V toward the anodic direction, reaching 0.75V vs. RHE. Solar cell made of identical structure (Mo/CuInS 2 /CdS/ZnO/ITO) showed power conversion efficiency of 2.1% with short-circuit photocurrent density and open circuit voltage of 7.4mA.cm -2 and 820mV, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Toward a high-voltage fast-charging pouch cell with TiO 2 cathode coating and enhanced battery safety

Nickel-rich layered lithium transition metal oxides, LiNi x Co y Mn 1-x-y O 2 , are key cathode materials for high-energy lithium-ion batteries owing to their high specific capacity. However, the commercial deployment of nickel-rich oxides has been hampered by their poor thermostability and insufficient cycle life. In this work full batteries with uncoated and TiO 2 -coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathodes and graphite anodes are compared in terms of electrochemical performance and safety behavior. The battery using a TiO 2 -coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathode exhibited better cyclic performance at high cutoff voltage. Electrochemical impedance spectroscopy analysis indicated that the TiO 2 -coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathode gave the battery a more stable charge transfer resistance. Transmission electron microscopy demonstrated that TiO 2 coating reduced accumulation of the cathode electrolyte interface layer on the particle surface. Time-of-flight secondary ion mass spectrometry demonstrated that TiO 2 coating markedly enhanced the interface stability of the cathode particle and protected the particle from serious etching by the electrolyte. Accelerating rate calorimetry revealed that the trigger temperature of thermal runaway for the battery using TiO 2 -coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 as cathode material was 257 °C, which was higher than that of the battery with the uncoated LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathode (251 °C). In situ X-ray diffraction during heating demonstrated that this enhanced safety can be attributed to the suppressed phase evolution of the coated cathode material.

25 ENERGY STORAGE↗

Copper iodide nanoparticles as a hole transport layer to CdTe photovoltaics: 5.5 % efficient back-illuminated bifacial CdTe solar cells

We report the role of copper iodide (CuI) nanoparticles (NPs) as a hole transport layer (HTL) in cadmium sulfide/cadmium telluride (CdS/CdTe) photovoltaics. These CuI NPs were prepared using solution processing at room temperature and used to fabricate monofacial and bifacial CdTe solar cells with different back contacts. Using CuI/Au as the back contact, the device efficiency reached to 14.8% with outstanding fill factor (FF) of 79.2%. Replacing the gold (Au) electrode with sputtered transparent indium tin oxide (ITO), a CuI/ITO back contact yielded photoconversion efficiencies (PCEs) of 11.6% and 5.5% under front and back illumination respectively. Bifacial devices (CdTe/ITO) without the CuI NP HTL have an efficiency of 7.0% and 1.0% for front and back illumination, respectively. For CuI/ITO, a current collection of 12.0 mAcm -2 was observed upon back illumination which significantly improved over an ITO-only back contact (5.0 mAcm -2 ). The PCE obtained from back illumination was enhanced when using CuI NPs as the HTL due to the reduced back barrier height, and improved back interface as determined by temperature dependent current vs. voltage characteristics and impedance spectroscopy analysis. The improvement in device performance of the bifacial configuration is a significant step forward toward realizing thin film photovoltaic modules which harvest energy incident on the rear of the module.

36 MATERIALS SCIENCE↗

Bi-cross validation of spectral clustering hyperparameters

One challenge impeding the analysis of terabyte scale X-ray scattering data from the Linac Coherent Light Source (LCLS) is determining the number of clusters required for the execution of traditional clustering algorithms. Here, we demonstrate that the previous work using bi-cross validation to determine the number of singular vectors directly maps to the spectral clustering problem of estimating both the number of clusters and hyperparameter values. Here by applying this method to LCLS X-ray scattering data enables the identification of dropped shots without manually setting boundaries on detector fluence and provides a path toward identifying rare and anomalous events.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Estimating the Likelihood of GHG Concentration Scenarios From Probabilistic Integrated Assessment Model Simulations

The climate scenarios that form the basis for current climate risk assessments have no assigned probabilities, and this impedes the analysis of future climate risks. This paper proposes an approach to estimate the probability of carbon dioxide (CO 2 ) concentration scenarios used in key climate change modeling experiments. It computes the CO 2 emissions compatible with the concentrations prescribed by Coupled Model Intercomparison Project Phase 5 (CMIP5) and CMIP6 experiments. The distribution of these compatible cumulative emissions is interpreted as the likelihood of future emissions given a concentration pathway. Using Bayesian analysis, the probability of each pathway can be estimated from a probabilistic sample of future emissions. The approach is demonstrated with five probabilistic CO 2 emission simulation ensembles from four Integrated Assessment Models (IAM), leading to independent estimates of the likelihood of the CO 2 concentration of Representative Concentration Pathways (RCP) and Shared Socioeconomic Pathways (SSP). Results suggest that SSP5-8.5 is unlikely for the second half of the 21st century, but offer no clear consensus on which of the remaining scenarios is most likely. Estimates of likelihoods of CO 2 concentrations associated with RCP and SSP scenarios are affected by sampling errors, differences in emission sources simulated by the IAMs, and a lack of a common experimental framework for IAM simulations. These shortcomings, along with a small IAM ensemble size, limit the applicability of the results presented here. Novel joint IAM and the Earth System Model experiments are needed to deliver actionable probabilistic climate risk assessments.

54 ENVIRONMENTAL SCIENCES↗

A Perspective on Traditional and Data Driven Electrochemical Modeling and Analysis

To understand the behavior of electrochemical systems, we need to reduce the dimensionality of the measured current-voltage-time (I-V-t) data by fitting models, thus enabling us to analyze and compare the governing physics. Traditionally, the process for this is an 'expert first' approach: defining the model and its explicit assumptions based on inductive reasoning or empirical observation, fitting small portions of the I-V-t data where assumptions are most valid or carefully designing experiments to enforce key assumptions, and then interpreting the model parameters. However, modern data-driven methods enable a new paradigm: a 'data first' approach, where the latent behaviors governing the system's measured response are identified directly using machine-learning models that optimize both model structure and parameters from the I-V-t data, guaranteeing that the learned model explains as much of the observed system response as possible. After model identification, the model can then be interrogated by an expert to connect observed behaviors with underlying physics. This talk will review several different types of electrochemical analysis (electrochemical impedance, differential voltage-capacity, electrochemical kinetics) and compare the traditional and data-driven methods for analyzing the data.

42 ENGINEERING↗