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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Non‐Linear Kinetics of The Lithium Metal Anode on Li 6 PS 5 Cl at High Current Density: Dendrite Growth and the Role of Lithium Microstructure on Creep

Abstract Interfacial instability, viz., pore formation in the lithium metal anode (LMA) during discharge leading to high impedance, current focusing induced solid–electrolyte (SE) fracture during charging, and formation/behaviour of the solid–electrolyte interphase (SEI), at the anode, is one of the major hurdles in the development of solid‐state batteries (SSBs). Also, understanding cell polarization behaviour at high current density is critical to achieving the goal of fast‐charging battery and electric vehicle. Herein, via in situ electrochemical scanning electron microscopy (SEM) measurements, performed with freshly deposited lithium microelectrodes on transgranularly fractured fresh Li6PS5Cl (LPSCl), the LiǀLPSCl interface kinetics are investigated beyond the linear regime. Even at relatively small overvoltages of a few mV, the LiǀLPSCl interface shows non‐linear kinetics. The interface kinetics possibly involve multiple rate‐limiting processes, i.e., ion transport across the SEI and SE|SEI interfaces, as well as charge transfer across the LiǀSEI interface. The total polarization resistance R P of the microelectrode interface is determined to be ≈ 0.8 Ω cm 2 . It is further shown that the nanocrystalline lithium microstructure can lead to a stable LiǀSE interface via Coble creep along with uniform stripping. Also, spatially resolved lithium deposition, i.e., at grain surface flaws, grain boundaries, and flaw‐free surfaces, indicates exceptionally high mechanical endurance of flaw‐free surfaces toward cathodic load (>150 mA cm −2 ). This highlights the prominent role of surface defects in dendrite growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Mitigating Battery Cell Failure: Role of Ag‐Nanoparticle Fillers in Solid Electrolyte Dendrite Suppression

Abstract The development of solid‐state batteries (SSBs) with lithium Li metal anodes holds significant promise for enhancing the energy density and safety of next‐generation energy storage systems. However, their commercialization is hindered by challenges related to Li dendrite formation, which can lead to short circuits and battery failure. In this study, the role of Ag nanoparticles embedded within solid electrolytes (SE) is investigated in suppressing dendrite propagation. The results demonstrate that Ag nanoparticles effectively mitigate two key failure mechanisms: (1) dendrite growth within porous networks at low current densities and (2) stress intensification‐induced SE fracture at higher current densities (12 mA cm −2 ). Ex situ characterization using focused‐ion beam – scanning electron microscopy (FIB–SEM) and energy dispersive X‐ray spectroscopy (EDS,) reveals that Ag nanoparticles migrate alongside advancing Li dendrites, promoting homogeneous dendrite growth and reducing the likelihood of localized stress concentrations. Additionally, the incorporation of Ag nanoparticles is shown to facilitate a more uniform Li distribution toward the anode side, which can potentially enable the use of higher charging rates in SSBs. This study provides a new perspective on Li dendrite suppression and presents new opportunities for enhancing the performance and safety of SSBs.

Diallo, Mouhamad Said↗
NASA NTRSDate not supplied

Imdr Regio: The Geology of A Possible Active Hot Spot on Venus and A Target for Future Exploration By the ESA Envision Mission.

With Venus being the focus of future new missions like ESA’s EnVision, we need to look for target sites for future investigations on Venus. The different instruments will help to study the planet in a unprecedented detail. In particular, the VenSAR instrument will map the 20% of the surface of Venus at a resolution of 5 to 10 meters/pixel, so it gets crucial to select what areas of Venus deserve to be targeted for such a high-resolution mapping. We propose here Imdr Regio as a good candidate location for combined high resolution SAR mapping and for study with the rest of the mission instruments (e.g., Subsurface Radar Sounder). Imdr Regio is a large topographic rise that extends approximately from 35ºS-50ºS and 195ºE-225ºE between the volcanic plains of Helen, Nsomeka and Wawalag Planitiae. Imdr Regio was classified as a volcano-dominated topographic rise with a minimum-maximum diameter of 1200-1400 km and a swell height of 1.6 km. The southeast of Imdr Regio is dominated by Idunn Mons (46.5ºS/214.5ºE). Studies using the 1 µm (derived) surface emissivity from the Venus Express mission of the volcanic flows surrounding Idunn Mons suggest that high emissivity values in the volcano flanks are related to relatively unweathered basaltic rock and therefore indicative of a recent or even ongoing volcanic activity. We have carried out geologic mapping in the area to constrain volcanic and tectonic structures, and the geologic history of the large topographic rise. This geologic mapping reveals that different styles of volcanism are present across Imdr Regio and that this volcanic activity takes place in all the hot spot in close relation with the formation of a rift throughout all time represented by in the area. The first stages on the evolution of this large volcano are characterized by the formation of a radial fracture system and contemporaneous large sheet flows. These large sheet flows are locally difficult to distinguish from regional plains and are also deformed by regional N-trending wrinkle ridges. After this initial phase, multiple overlapping digitate flow units form the flanks and summit of the volcano and are contemporaneous with NW-SE trending fractures and graben of Olapa Chasma, a rift system that cross the topographic rise. To the northwest another large volcano also presents a system of radial fractures but lacks clear large sheet flows. Numerous pit chains are associated to fractures and graben, suggesting that transport of magma under the surface is important. The geologic history based on the mapping suggests that activity in Imdr Regio started with the emplacement of a plume/diapir in the southeast, which resulted in the formation of a radial dyke system and the emplacement of large sheet flows in Idunn Mons. The presence of other large volcanoes to the northwest suggests the presence of another magmatic source (plume or diapir). After this initial stage, volcanism continues in Idunn Mons and activity in the topographic rise is strongly related to the formation of Olapa Chasma. Rift-related volcanic flows postdate these other volcanoes and are contemporaneous with the late activity in Idunn Mons. Monogenetic volcanism is present in the rift and in all the units that are in the area.

I. López↗
DOE OSTI2021

Understanding metal propagation in solid electrolytes due to mixed ionic-electronic conduction

Metal penetration into a solid electrolyte (SE) is one of the critical problems impeding the practical application of solid-state batteries. In this study, we investigate the conditions under which electronic conductivity of the SE can lead to metal deposition and fracture within the SE. Three different stages for void filling (metal plating initiation, metal growth, and metal compression) in the SE are identified. We show that a micron-size isolated void in the SE near the anode can be quickly filled in by metal and fractured when the developed pressure in the void grows larger than the maximum pressure the SE material can sustain. We find that the anode voltage and applied current density play a significant role in determining the vulnerability to metal deposition. We discuss several strategies to prevent electronic conductivity-driven metal propagation in electrolytes that are not fully dense, including the densified layers between the anode and SE.

25 ENERGY STORAGE↗
DOE OSTI2025

Minimization of Cathode|Solid-Electrolyte Interfacial Delamination through the Application of Interphase Layers

Next-generation lithium-ion batteries are expected to use solid electrolytes (SEs) to enable higher energy density and extreme fast-charge capabilities. One major mode of degradation at the cathode|SE interface is delamination between the cathode active materials and SEs, which leads to performance decay. Experimental observations indicate that implementation of interphase layers can minimize the cathode|SE delamination induced capacity fade. A multiscale computational methodology is developed here to investigate the applicability of boron substituted lithium carbonate (Li 2+x B x C 1–x O 3 , x = 0.5, or LBCO) to minimize the delamination at the cathode|SE interface. Atomistic simulations indicate that the fracture energies at both the cathode|LBCO and LBCO|SE interfaces are higher than those at the cathode|SE interface, which reduces the extent of delamination. Mesoscale simulations indicate that, apart from increasing the fracture energy, decreasing the evolution of strain energy by lowering the elastic modulus of the interphase layer can also minimize the extent of delamination at the cathode|SE interface. However, the adoption of an interphase layer with high ionic conductivity is necessary to minimize the ohmic losses during operation at higher current densities. This study provides guidance on selecting interphase layers with specific properties and thicknesses to minimize both interfacial delamination and impedance growth.

LBCO↗
NASA NTRS1976

Development of techniques to simplify the process of investigation and estimate of natural resources in remote and relatively unexplored areas, Venezuela

The author has identified the following significant results. Based upon the results obtained by both interpretations, radar and satellite, highly fractured zones were outlined and checked against geologic rock samples. Most of the rock samples were collected along the Ventuari River that crosses most of the project area from NE to SE. The structural orientation and fracture patterns were taken into consideration during the planning of flight lines, also the magnetic declination of the area. Most of the flight lines were oriented N 30 deg W across known structural trends; the altitude above ground was 450 feet, and the distance between lines was 3000 feet. The ERTS image permits the obtention of a panoramic vision of the area, and facilitates the exact delineation of major drainages. Topographic changes are easily observed. Rocky outcrops are easily distinguishable on band 5 and 7. Shrub vegetation zones are distinguishable on both bands, without possible separation of forest types, this is possible only when the physiographic conditions of small textural differences are taken into account.

Romero, A. C.↗
DOE OSTI2022

Tuscaloosa Marine Shale: Seal or Source? Petrophysical Comparative Study of Wells in SE Louisiana and SW Mississippi

The Tuscaloosa Marine Shale (TMS) is a versatile Late Cretaceous shale formation present in central and SE Louisiana and SW Mississippi, which drew attention because of the various roles played within the Tuscaloosa Group. In this paper, it is debated whether the Tuscaloosa Marine Shale can act as a source, reservoir, or seal all throughout the shale play or only in certain areas. Well log and core data from Adams County, Mississippi, are compared to data from East Feliciana Parish in Louisiana. Conclusions were drawn based on the results of well log analysis, X-ray Diffraction (XRD), porosity–permeability measurements, programmed pyrolysis, and fracture analysis. It was shown that the Tuscaloosa Marine Shale interval in SE Louisiana consists of important amounts of calcite, exhibits multiple natural fractures, has porosity values as high as 9.3%, and shows a TOC content of up to 2.8 wt%. On the other hand, samples from a well at the Cranfield field, MS, are characterized by considerably lower TOC values of around 0.88 wt%, porosities between 0.33% and 4%, and no serious fracturing. The formation demonstrates better reservoir and source potential in SE Louisiana and reliable CO2 sealing capacity in SW Mississippi. The analysis presented in this paper represents a holistic approach to the characterization of shale formations, is applicable to other plays around the world, and can be used as an integral part of CO2 sequestration or hydraulic fracturing programs.

04 OIL SHALES AND TAR SANDS↗
DOE OSTI2021

Direct Observation of Interfacial Mechanical Failure in Thiophosphate Solid Electrolytes with Operando X-Ray Tomography

Herein, the mechanical behaviors of Li 10 GeP 2 S 12 (LGPS) solid electrolytes during electrochemical cycling using operando X-ray tomography are investigated. It is demonstrated that the bulk mechanical decomposition of LGPS when cycled against lithium is a direct result of electrochemical reduction of the solid electrolyte at the LGPS/Li 0 interface. The reductive decomposition of LGPS during lithium plating results in the formation of low-density domains at the electrode/electrolyte interface, which impose sufficient mechanical stress on the underlying LGPS to crack the SE pellet. The critical stress developed prior to pellet fracture is significantly lower than the bulk shear modulus of LGPS, suggesting that the electrochemical instability of LGPS dramatically worsens the mechanical stability of the material near the LGPS/Li 0 interface. It is also shown that the application of a highly concentrated liquid electrolyte to the LGPS surface suppresses the reductive decomposition of LGPS, improving both the electrochemical performance and mechanical stability of the bulk LGPS solid electrolyte.

36 MATERIALS SCIENCE↗
NASA NTRS2018

ASTM E399 Standard Development - KIsi Analysis Method

The ASTM E399 test method is used to determine the plane‐strain fracture toughness, K (sub IC), for metallic materials. The test consists of monotonically loading a pre-cracked test specimen to failure while recording the applied load and the crack mouth opening displacement. Several test specimen types are allowable per ASTM E399; two common geometries are the compact tension (C(T)) and the single-edge bend (SE(B)) geometries. The test result is an estimate of the plane‐strain fracture toughness, K (sub q), determined by the intercept of the test record with a 95 percent secant-offset construction line. The 95 percent offset represents crack extension corresponding to approximately 2 percent of the original specimen ligament (assuming that all compliance change is the result of crack extension). If the test meets certain validity requirements based on specimen size and test behavior, the result is valid, and K (sub q) equals K (sub IC).

Tilson, William G.↗
DOE OSTI2023

Mechanical Properties of 2D LiInP 2 Se 6 : Implication for Semiconductor Applications

Metal phosphorus trichalcogenides (MPTCs) are emerging 2D semiconductor materials with unique functional properties that set them apart from other 2D systems. Despite the importance of their mechanical properties for improving the semiconductor device’s durability and performance, as well as for utilizing strain effects to customize material properties and create new functionality, our current understanding of MPTCs’ mechanical behavior is lacking and lags behind our knowledge of their other properties. Here, we use LiInP 2 Se 6 as a model example of MPTCs and report the first experimental measurements of the elastic and plastic (fracture) properties along both in-plane and out-of-plane directions by atomic force microscopy and nanoindentation. Being a 2D material that is entirely inorganic, LiInP 2 Se 6 surprisingly exhibits mechanical properties that resemble those of hybrid organic–inorganic materials rather than pure inorganic 2D materials. It has a soft crystal structure with low elastic moduli, a low difference in in-plane vs out-of-plane mechanical properties, and a combination of elastic and plastic characteristics of hybrid organic–inorganic materials. Furthermore, our work provides the mechanical information critically needed to mitigate and/or harness the strain effects in LiInP 2 Se 6 -based semiconductor devices and sheds light on the mechanical behaviors of MPTCs with indispensable insights.

2D semiconductor↗
NASA NTRS1987

Geometry and relative age of large patterned fractures in southern Acidalia Planitia, Mars

Extraordinary patterned fractures occur in Elysium, Utopia, and Acidalia Planitiae of Mars. Theories as to their origin range from permafrost patterning to tectonic fracturing. Recent studies indicate the patterned fractures may be a surface reflection of rough, buried terrane in which fracturing occurs as a result of differential compaction. The patterned terrane in the southern portion of the Acidalia region (MC4-SE, MC4-SC) is being studied to determine its age relative to other terranes and events, and to constrain models for the origin of the fractures. Fracturing in this area occurs between 5 and 25 degrees west longitude and 37 and 50 degrees north latitude. Many fracture patterns are roughly polygonal, with polygons ranging in size from approximately 11 to 32 km in diameter. Fracture traces range from the limit of resolution (10's of meters) to 35 km in length.

Borrello, Murray C.↗
NASA NTRS1983

Structure of the Saint Francois Mountains and surrounding lead belt, south east Missouri: Inferences from thermal IR and other data sets

Several digital data sets were registered to a common base map for southern Missouri. These registered data sets were examined in an attempt to improve our understanding of the crustal structure and the relationships between structure and Pb-Zn-Cu, Fe, Mn, and Ba ores in the area. Data included land station reading of gravity, geologic data, and Heat Capacity Mapping Mission (HCMM) images. The HCMM day infrared (IR) images of Missouri displayed linear features, which parallel a newly discovered NW-SE trending Bouguer gravity low. The structural pattern over the gravity low suggests vertical uplift of the low density crust via isostatic readjustment and consequent fracturing of the Paleozoic sedimentary cover. The presence of a gravity low is interesting because rifts are often sites of extensive mineralization. The HCMM thermal data were also examined in conjunction with digital topography, land use, and LANDSAT MSS data to understand the phenomena that produce linears on the HCMM day IR images. Finally, the kinds of information that can be extracted from day-night IR pairs are discussed.

Arvidson, R. E.↗
DOE OSTI2021

Lithium Deposition-Induced Fracture of Carbon Nanotubes and Its Implication to Solid-State Batteries

The increasing demand for safe and dense energy storage has shifted research focus from liquid electrolyte-based Li-ion batteries toward solid-state batteries (SSBs). However, the application of SSBs is impeded by uncontrollable Li dendrite growth and short circuiting, the mechanism of which remains elusive. Herein, we conceptualize a scheme to visualize Li deposition in the confined space inside carbon nanotubes (CNTs) to mimic Li deposition dynamics inside solid electrolyte (SE) cracks, where the high-strength CNT walls mimic the mechanically strong SEs. We observed that the deposited Li propagates as a creeping solid in the CNTs, presenting an effective pathway for stress relaxation. When the stress-relaxation pathway is blocked, the Li deposition-induced stress reaches the gigapascal level and causes CNT fracture. Mechanics analysis suggests that interfacial lithiophilicity critically governs Li deposition dynamics and stress relaxation. Furthermore, our study offers critical strategies for suppressing Li dendritic growth and constructing high-energy-density, electrochemically and mechanically robust SSBs.

25 ENERGY STORAGE↗
DOE OSTI2024

Comparison of Geochemical Reactivity of Marcellus and Caney Shale Based on Effluent Analysis

ABSTRACT: In this comparative study, we analyzed the changes in elemental concentrations of hydraulic fracturing fluids after interaction with the Marcellus and Caney Shale formations. The focus was on assessing the inherent risks and environmental implications associated with flowback waters, including their impact on soil, ground, and drinking water quality, and human health safety. The chemical compositions of effluents were determined through Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) and Mass spectrometry (ICP-MS). The Marcellus Shale, showed concentrations of Cd, averaging 0.380 ppm far exceeding safe water thresholds. Significant levels of As, Se, B, and Pb were detected in both shales, raising concerns about soil and water contamination. Analyzing the effluents from representative samples of sections of the Marcellus (S2 and S7) and Caney (R1 and R2) indicates different geochemical responses over 4 weeks of experiments. This comparison underscores the chemical changes and environmental considerations linked to hydraulic fracturing across shale formations, suggesting the value of tailored monitoring and regulatory measures for each type. 1. INTRODUCTION The Caney and Marcellus shales, differing in geology and geochemistry, represent distinct unconventional reservoirs. The Caney shale, is more ductile, with higher produced water volumes, (Smith et al., 2022) contrasts with the brittle Marcellus shale known for lower brine production but significant data availability. This study aims to elucidate the possible environmental health and safety issues that may arise from the hydraulic fracturing processes. The interaction between fracturing fluids and clays presents a significant challenge. The primary base of these fluids is water, which, when introduced to clay, can induce swelling and constrict flow pathways. This phenomenon is attributed to water molecules infiltrating the layers of clay, particularly in 2:1-type clays, leading to an increased distance between layers. To counteract this, clay stabilizers are employed (Awejori et al., 2021). Despite their effectiveness, these stabilizers are considered temporary solutions. Upon completion of the fracturing process, a concomitant amount of contaminated waters (flow back), with varied content is collected at the surface. From these, we can infer the geochemical reactions and the environmental challenges associated with these waters. Flowback waters can be reinjected or used for other purposes such as irrigation. This requires adequate screening and treatment for safe use.

Dje, L. B.↗
DOE OSTI2025

Morphological Heterogeneity Impact of Film Solid-State Cathode on Utilization and Fracture Dynamics

Structural heterogeneity in solid-state batteries can impact material utilization and fracture mechanisms. Crystallographically oriented lithium cobalt oxide film cathodes serve as a model electrode system for exploring how void distribution contributes to stress relief and build up during cycling. Real- and reciprocal-space operando and ex situ synchrotron based experiments are utilized to understand structural changes across multiple length scales contribute to stress generation and fracture. Nanotomography uncovers a depth-dependent porosity variation in the pristine electrode and highlights preferential fracture in regions of lower porosity during delithiation. Energy-dispersive X-ray diffraction and 3D X-ray absorption near-edge spectroscopy (XANES) reveal the underutilization of cathode material in these regions. 3D XANES also confirms preferential delithiation near the sub-grain boundaries. Chemo-mechanical modeling coupled with site-specific mechanical characterization demonstrate how stress accumulation in dense regions of the electrode leads to fracture and underutilization of active material. In conclusion, our findings reveal the importance of materials design to alleviate stress in small-volume changing cathodes.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Chemo-Mechanical Behavior and Stability of High-Loading Cathodes in Solid-State Batteries

Solid-state batteries can offer higher energy density and improved safety compared to lithium ion batteries, which use flammable liquid electrolytes. Increasing the ratio of cathode active materials in composite cathodes enhances the energy density and reduces manufacturing costs. Changes in the ratio of cathode active materials alter the microstructure and chemo-mechanical response of a cathode during operation. Understanding the relationship between composition, microstructure, and chemo-mechanical interactions is critical for optimizing solid-state cathodes. Here, in this study, we engineered composite cathodes with varying ratios of LiNi 0.8 Co 0.1 Mn 0.1 O 2 and Li 6 PS 5 Cl to systematically investigate the role of microstructural evolution in long-term chemo-mechanical transformations. Chemo-mechanical stresses resulting from the volume changes of the cathode active materials led to degradation mechanisms, such as fracture and interfacial delamination. Active material fracture and delamination led to underutilization of active material and significant capacity decay during cycling. Coatings that suppress active material-active material interactions during cycling may aid in suppressing the generation of local stress hotspots.

36 MATERIALS SCIENCE↗
NASA NTRS2015

Fracture Growth Testing of Titanium 6AL-4V in AF-M315E

The Green Propellant Infusion Mission (GPIM) will demonstrate the performance of AF-M315E monopropellant in orbit. Flight certification requires a safe-life analysis of the titanium alloy fuel tank to ensure inherent flaws will not cause failure during the design life. Material property inputs for this analysis require testing to determine the stress intensity factor for environmentally-assisted cracking (K (sub EAC)) of Ti 6Al-4V in combination with the AF-M315E monopropellant. Testing of single-edge notched specimens SE(B) representing the bulk tank membrane and weld material were performed in accordance with ASTM E1681. Specimens with fatigue pre-cracks were loaded into test fixtures so that the crack tips were exposed to the monopropellant at 50 degrees Centigrade for a duration of 1,000 hours. Specimens that did not fail during exposure were opened to inspect the crack surfaces for evidence of crack growth. The threshold stress intensity value, KEAC, is the highest applied stress intensity that produced neither a failure of the specimen during the exposure nor showed evidence of crack growth. The threshold stress intensity factor of the Ti 6Al-4V forged tank material when exposed to AF-M315E monopropellant was found to be at least 22.0 kilopounds per square inch. The stress intensity factor of the weld material was at least 31.3 kilopounds per square inch.

AF-M315E↗