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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Exploring cycling induced crystallographic change in NMC with X-ray diffraction computed tomography

This study presents the application of X-ray diffraction computed tomography for the first time to analyze the crystal dimensions of LiNi 0.33 Mn 0.33 Co 0.33 O 2 electrodes cycled to 4.2 and 4.7 V in full cells with graphite as negative electrodes at 1 μm spatial resolution to determine the change in unit cell dimensions as a result of electrochemical cycling. The nature of the technique permits the spatial localization of the diffraction information in 3D and mapping of heterogeneities from the electrode to the particle level. An overall decrease of 0.4% and 0.6% was observed for the unit cell volume after 100 cycles for the electrodes cycled to 4.2 and 4.7 V. Additionally, focused ion beam-scanning electron microscope cross-sections indicate extensive particle cracking as a function of upper cut-off voltage, further confirming that severe cycling stresses exacerbate degradation. Finally, the technique facilitates the detection of parts of the electrode that have inhomogeneous lattice parameters that deviate from the bulk of the sample, further highlighting the effectiveness of the technique as a diagnostic tool, bridging the gap between crystal structure and electrochemical performance.

25 ENERGY STORAGE↗
DOE OSTI2024

Effects of catholyte aging on high-nickel NMC cathodes in sulfide all-solid-state batteries

Sulfide solid-state electrolytes (SSEs) in all-solid-state batteries (SSBs) are recognized for their high ionic conductivity and inherent safety. The LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathode offers a high thermodynamic potential of approximately 3.8 V vs. Li/Li + and a theoretical specific capacity of 200 mA h g −1 . However, the practical utilization of NMC811 in sulfide SSBs faces significant interfacial challenges. The oxidation instability of sulfide solid electrolytes against NMC811 and the formation of the cathode electrolyte interphase (CEI) during cycling lead to degradation and reduced cell performance. Volumetric changes in NMC during lithiation and de-lithiation can also cause detachment from sulfide electrolytes or internal particle cracking. Despite extensive galvanostatic cycling studies to address the issues, the calendar life of sulfide SSBs remains poorly understood. Here, we systematically studied the effects of four different catholytes on the calendar aging of LiNbO 3 (LNO)-coated NMC811, including Li 6 PS 5 Cl (LPSCl), Li 3 InCl 6 –Li 6 PS 5 Cl (LIC–LPSCl), Li 3 YCl 6 –Li 6 PS 5 Cl (LYC–LPSCl), and Li 10 GeP 2 S 12 (LGPS). Our results indicate that LPSCl provides optimal capacity retention when stored at high state-of-charge (SOC) at room temperature, but the LIC–LPSCl cathode shows significant capacity degradation and chemical incompatibility. We also established an effective electrochemical calendar aging testing protocol to simulate daily usage, enabling quick inference of the calendar life of SSBs. In conclusion, this new testing approach accelerates materials selection strategies for high-nickel NMC composite cathodes in sulfide SSBs.

25 ENERGY STORAGE↗
DOE OSTI2023

Quantifying Aging-Induced Irreversible Volume Change of Porous Electrodes

Automotive manufacturers are working to improve cell and pack design by increasing their performance, durability, and range. One of the critical factors to consider as the industry moves towards materials with higher energy density is the ability to consider the irreversible volume change characteristic of the accelerated SEI layer growth tied to the large volume change and particle cracking typically associated with active material strain. As the time from initial design to manufacture of electric vehicle is decreased in order to rapidly respond to consumer demands and widespread adoption of electric vehicles, the ability to link aging and volume change to end of life vehicle requirements using virtual tools is critical. In this study, apply a mechano-electrochemical model to determine the irreversible volume change at the electrode and cell level, allowing for virtual design iterations to predict the volume change at battery cell aged states.

Electrochemistry↗
DOE OSTI2024

Capacity Fade of Graphite/NMC811: Influence of Particle Morphology, Electrolyte, and Charge Voltage

LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) is an important Li-ion battery cathode material; however, there is a tradeoff between delivered capacity and capacity retention. As the charge potential increases the capacity rises but at the expense of capacity retention. The decrease in capacity retention has been ascribed to several factors including particle cracking, surface reconstruction, transition metal dissolution, and electrolyte reactivity. The present study compares 4.1 and 4.3 V charging limits in commercially relevant graphite/NMC811 pouch cells for single crystal (SC) and polycrystalline (PC) NMC811 with ethylene carbonate (EC)-containing or EC-free electrolytes. The electrochemistry is rationalized through analysis of electrochemical impedance spectroscopy, positive electrode X-ray photoelectron spectroscopy, soft X-ray absorption spectroscopy, X-ray diffraction, and negative electrode mapping by X-ray fluorescence. Graphite/SC-NMC811 cells show high-capacity retention at 4.1 V but exhibit degradation at 4.3 V charging potentials. The EC-free electrolyte cells led to higher capacity fade, especially when charged to 4.3 V. Cathode dissolution and deposition on the negative electrode from PC-NMC811 cells was higher than for samples from SC-NMC811 cells. This study reveals the impact of material type, charge voltage, and electrolyte composition on the reactions at the positive electrode, their influence on the negative electrode, and evolution with cycle number.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Physical Interpretation of Early Battery Life Prediction Models

Early battery life prediction models are most useful for R&D if they help us understand the early changes in battery electrochemical response that correspond with long-term degradation and failure. Linear regression models such as Fused lasso and Partial Least Squares can fit coefficients directly to high-dimensional electrochemical data like capacity-voltage and ΔV–state-of-charge, i.e., Q(V) and ΔV(SOC) curves, learning coefficients that can be physically interpreted. We leverage the ISU-ILCC battery aging data set to learn high-dimensional coefficients for early battery life prediction from traditional slow-rate capacity check data, demonstrating learning on Q(V), d Q· d V −1 , and ΔV(SOC) curves. A thorough study on the dependence of coefficient values on train/test size and data preprocessing methods is made, demonstrating the reliability of high-dimensional regression approaches unless very small amounts of data are used for model training. For this data set, coefficients from Q(V) and d Q· d V −1 models highlight changes in electrode stoichiometry due to lithium loss, while ΔV(SOC) coefficients highlight changes in positive electrode diffusivity due to particle cracking as well as electrode stoichiometry shifts. By directly interpreting the coefficients of a regression model, we make physical insights into battery degradation mechanisms without requiring the assumptions of traditional battery data analysis methods.

25 ENERGY STORAGE↗
DOE OSTI2024

Rapid Electrochemical Diagnosis of Battery Health and Safety from Cells to Modules

Rapid electrochemical diagnosis of battery health and failure is critical for ensuring reliable battery performance and battery safety. Traditional battery health diagnostics such as capacity measurements and DC pulse tests are reliable and well-understood, however, these measurements of battery capacity and resistance do not capture all aspects of battery degradation. Other aspects of degradation, such as electrolyte decomposition, lithium-plating, and particle cracking are difficult to detect electrochemically but are crucial to measure to get a full picture of battery safety and flag out potential failures. In this work, lab- and field-aged commercial lithium-ion batteries and modules of various chemistries and formats are tested using a variety of traditional electrochemical characterization methods as well as using 2-minute pseudo-random DC pulse sequences at rest and during charge/discharge. The electrochemical measurements are compared to physical cell measurements, cell efficiency, drive cycle performance, physical and thermal heterogeneity, and qualitative safety metrics using statistical and machine-learning methods to discover if a comprehensive "battery health map" can be accurately identified using only rapid DC measurements.

ADVANCED PROPULSION SYSTEMS,ENERGY STORAGE↗
DOE OSTI2020

High capacity and stable cathode materials

High energy density cathode materials, such as LiNixMnyCozO2 (NMC) cathode materials, with improved discharge capacity (hence energy density) and enhanced cycle life are described. A solid electrolyte, such as lithium phosphate infused inside of secondary particles of the cathode material demonstrates significantly enhanced structural integrity without significant or without any observable particle cracking occurring during charge/discharge processes, showing high capacity retention of more than 90% after 200 cycles at room temperature. In certain embodiments the disclosed cathode materials (and cathodes made therefrom) are formed using nickel-rich NMC and/or are used in a battery system with a non-aqueous dual-Li salt electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2023

Failure analysis of nuclear transient-tested UN tristructural isotropic fuel particles in a 3D printed SiC matrix

Fully ceramic microencapsulated fuel elements containing UN tristructural isotropic (TRISO) fuel particles within a 3D printed SiC matrix were subjected to transient testing with varying energy depositions. Detailed post-irradiation examinations were performed, including leaching in hot HNO3 and post-leaching X-ray computed tomography, to quantify the percentage of failed TRISO particles and crack propagation within the particles and surrounding fuel matrix. In parallel, detailed finite element analyses were performed for comparison with experimental findings and to better evaluate transient failure modes. The lowest transient energy deposition—which still exceeded bounding values for high-temperature gas-cooled reactor applications—resulted in no detectable TRISO particle failures or matrix cracking, which was consistent with the simulations. Simulations of the higher-energy transients for which significant TRISO particle failure was expected were generally able to reproduce the transient temperatures and matrix cracking. Thus, the TRISO particle failures were explained based on the effects of local SiC matrix thickness and porosity. Results generally confirmed the high strength of the additively manufactured SiC matrix but also affirmed the need for a modified UN TRISO architecture to prevent SiC matrix cracks from propagating through TRISO layers. This unique failure mode has not historically been considered for TRISO fuels contained in weaker graphite matrices.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Stabilizing High–Nickel Cathodes with High–Voltage Electrolytes

Electrolytes connect the two electrodes in a lithium battery by providing Li + transport channels between them. Advanced electrolytes are being explored with high-nickel cathodes and the lithium-metal anode to meet the high energy density and cycle life goals, but the origin of the performance differences with different electrolytes is not fully understood. Here, the mechanisms involved in protecting the high-capacity, cobalt-free cathode LiNiO 2 with a model high-voltage electrolyte (HVE) are delineated. The kinetic barrier posed by a thick surface degradation layer with poor Li + -ion transport is found to be the major contributor to the fast capacity fade of LiNiO 2 with the conventional carbonate electrolyte. In contrast, HVE reduces the side reactions between the electrolyte and the electrodes, leading to a thinner nano-interphase layer comprised of more beneficial species. Crucially, the HVE leads to a different surface reorganization pathway involving the formation of a thinner nanoscale LiNi 2 O 4 spinel phase on the LiNiO 2 surface. Finally, with a high 3D Li + -ion and electronic conductivity, the spinel LiNi 2 O 4 reorganization nanolayer preserves fast Li + transport across the cathode–electrolyte interface, reduces reaction heterogeneity in the electrode and alleviates intergranular cracking within secondary particles, resulting in superior long-term cycle life.

25 ENERGY STORAGE↗
DOE OSTI2022

Nanotomographic observation and statistical analysis of overcharging induced cracks in LiCoO 2 single crystalline particles

Particle fracture represents an important mode of battery electrode degradation. Extensive cracking occurs in the layered oxide cathodes of lithium-ion rechargeable batteries when they are charged beyond safe operational voltages. In this paper, we analyze the morphology and distribution of cracks in over 100 overcharged LiCoO 2 (LCO) single-crystalline particles imaged via X-ray nanotomography. Herein, we observe a strong particle size dependence in both nucleation and growth of cracks, with percentage of cracked particles, crack size, and crack surface area per unit volume all increasing significantly with particle volume. Increasing the cutoff voltage above 4.6V is found to trigger much more pronounced crack growth, which we attribute to the large misfit stress caused by the H1-3 to O1 phase transition. This study offers valuable statistical insights into the fracture behavior of layered oxide cathodes and reveals the importance of particle size control on electromechanical degradation of battery electrodes.

25 ENERGY STORAGE↗
DOE OSTI2022

Assessing Long-Term Cycling Stability of Single-Crystal Versus Polycrystalline Nickel-Rich NCM in Pouch Cells with 6 mAh cm -2 Electrodes

Lithium-ion batteries based on single-crystal LiNi1-x-yCoxMnyO2 (NCM, 1-x-y ≥ 0.6) cathode materials are gaining increasing attention due to their improved structural stability resulting in superior cycle life compared to batteries based on polycrystalline NCM. However, an in-depth understanding of the less pronounced degradation mechanism of single-crystal NCM is still lacking. Here, a detailed postmortem study is presented, comparing pouch cells with single-crystal versus polycrystalline LiNi 0.60 Co 0.20 Mn 0.20 O 2 (NCM622) cathodes after 1375 dis-/charge cycles against graphite anodes. The thickness of the cation-disordered layer forming in the near-surface region of the cathode particles does not differ significantly between single-crystal and polycrystalline particles, while cracking is pronounced for polycrystalline particles, but practically absent for single-crystal particles. Transition metal dissolution as quantified by time-of-flight mass spectrometry on the surface of the cycled graphite anode is much reduced for single-crystal NCM622. Similarly, CO 2 gas evolution during the first two cycles as quantified by electrochemical mass spectrometry is much reduced for single-crystal NCM622. Benefitting from these advantages, graphite/single-crystal NMC622 pouch cells are demonstrated with a cathode areal capacity of 6 mAh cm -2 with an excellent capacity retention of 83% after 3000 cycles to 4.2 V, emphasizing the potential of single-crystalline NCM622 as cathode material for next-generation lithium-ion batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Multiscale Understanding of Surface Structural Effects on High-Temperature Operational Resiliency of Layered Oxide Cathodes

The worldwide energy demand in electric vehicles and the increasing global temperature have called for development of high-energy and long-life lithium-ion batteries (LIBs) with improved high temperature operational resiliency. However, current attention has been mostly focused on cycling aging at elevated temperature, leaving considerable gaps of knowledge in the failure mechanism and practical control of abusive calendar aging and thermal runaway that are highly related to the eventual operational lifetime and safety performance of LIBs. Herein, using a combination of various in situ synchrotron X-ray and electron microscopy techniques, we report a multiscale understanding of surface structure effects involved in regulating the high temperature operational tolerance of polycrystalline Ni-rich layered cathodes. Our results collectively show that an ultraconformal poly (3,4-ethylenedioxythiophene) coating can effectively prevent LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode from undesired phase transformation and transition metal dissolution on the surface, atomic displacement and dislocations within primary particles, intergranular cracking along the grain boundaries within secondary particles, and intensive bulk oxygen release during high state-of-charge and high temperature aging. As a result, the present work highlights the essential role of surface structure controls in overcoming the multiscale degradation pathways of high-energy battery materials at extreme temperature.

25 ENERGY STORAGE↗
NASA NTRS1989

Fracture toughness in SiC/Al composite material

Crack initiation fracture toughness does not depend on SiC particle size. Crack growth fracture toughness increases as the size of the SiC particle increases. The fracture process is confined to a very narrow band and takes place within the matrix. In the case of composite reinforced with SiC particles of 20 microns and above, fracture of SiC begins to dominate. The matrix is influenced by a triaxial tension in the matrix and a high density of dislocations generated at SiC/Al interfaces due to the difference in coefficient of thermal expansion between SiC and the Al matrix.

Flom, Y.↗
DOE OSTI2025

Micromechanical Properties of the SiC and Pyrolytic Carbon Layers in Tristructural-Isotropic Coated Particles

Tristructural isotropic (TRISO) coated particle fuel was initially developed for high temperature gas cooled reactors (HTGR) and has been proposed for several other advanced reactor concepts. The design of TRISO particles focuses on preventing the release of fission products in normal and off-normal reactor conditions. The particle design features an actinide bearing fuel kernel that is surrounded by three pyrolytic carbon (PyC) layers and a silicon carbide layer (SiC). The mechanical stability of the particle and fission product retention for both metallic and gaseous fission products depend on the SiC layer. Post irradiation examination (PIE) of TRISO fuel from the first two US DOE Advanced Gas Reactor Fuel Development and Qualification Program irradiation campaigns, AGR-1 and AGR-2, had identified a low rate of particles exhibiting cracking in the SiC layer that did not propagate across the SiC layer. While cracking in the SiC is rare for test conditions and particles associated with the AGR program, understanding the stress state and mechanical properties of the SiC and PyC layers related to particle architecture can aid predicting thermomechanical response of TRISO fuel under the prescribed operation envelope and beyond as well as aiding in the development of similar fuel concepts for other advanced reactors. The presented investigation shows the relationship of the mechanical properties and mechanical response (e.g., understanding crack propagation) of the SiC and PyC layers relative to position within the particle. Testing was conducted on the inner and outer PyC layers of TRISO particles to quantify differences in mechanical behavior.

Montoya, Katherine [ORNL] (ORCID:0000000326955086)↗
NASA NTRS1982

Creep of plasma-sprayed-ZrO2 thermal-barrier coatings

Specimens of plasma-sprayed-zirconia thermal-barrier coatings with three different porosities and different initial particle sizes were deformed in compression at initial loads of 6900, 13,800, and 24,100 kPa (1000, 2000, and 3500 psi) and temperatures of 1100, 1250, and 1400 C. The coatings were stabilized with lime, MgO, and two different concentrations of Y2O3. Creep began as soon as the load was applied and continued at a constantly decreasing rate until the load was removed. Temperature and stabilization had a pronounced effect on creep rate while the stress, particle size, and porosity had a lesser effect. Creep deformation was due to cracking and particle sliding.

Firestone, R. F.↗
DOE OSTI2022

Assessment of lignite upgrade and hydrogen evolution via electrolysis

Lignite, considered as the lowest-rank coal, accounts for 45% of the total coal resources worldwide, and its low carbon and high ash contents limit its large-scale application. In order to upgrade lignite effectively, a modified coal electrolytic cell (MCEC) was designed, built, and then evaluated for lignite upgrade and hydrogen production through electrolysis, and the operating conditions were optimized. The results show that the performance of the MCEC outperformed the previous coal electrolytic cell (CEC). The operating temperature and iron concentration significantly impact the average current density per milligram of catalyst (ACDMC). The content of dry fixed carbon and heating value increased by 20.9% (wt%) and 8.15%, respectively, in electrolyzed lignite compared with raw lignite. Besides, 71.5% ash and 39.6% mercury were removed from raw lignite after electrolysis, which is the first report. The Faradaic efficiency (FE) for hydrogen evolution reached 99% using MCEC. In addition, the analysis of spectroscopy methods (SEM, EDX, FTIR, and XRD) revealed that the lignite particles were cracked; the oxygen-containing functional groups increased; the minerals of quartz and hematite formed on the surface of lignite particles after electrolysis. Furthermore, the facts indicate that electrolysis of lignite is a competitive approach for lignite upgrade and hydrogen production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Quantifying the impact of operating temperature on cracking in battery electrodes, using super-resolution of microscopy images and stereology

There are numerous factors that can have an impact on the degradation behavior of batteries, such as the number of recharge cycles or the charge rate. Here, we investigate the influence of operating temperature on the structural degradation of the microstructure in lithium-ion positive electrodes. For that purpose, the microstructure is characterized for cathodes which have been cycled for 200 cycles under 6C (10-minute) charging at different operating temperatures, namely, 20°C, 30°C, 40°C, and 50°C. For each operating condition scanning electron microscopy (SEM) images of cross-sectioned Li x Ni 0.5 Mn 0.3 Co 0.2 O 2 (NMC532) electrodes have been analyzed, to determine structural descriptors such as global particle porosity, crack size/length/width distribution, and porosity and specific surface area distribution of individual particles. Additionally, a stereological method has been deployed to investigate the local particle porosity as a function of distance to the particle center. Results show that particle porosity increases with increasing cycling temperature. Particle porosity is greatest at the particle center and decreases along the particle radius to the exterior. Particle surface area is similar across the four cycling-temperature aging conditions.

25 ENERGY STORAGE↗