An Atomic View of Cation Diffusion Pathways from Single;#8208;Crystal Topochemical Transformations
Abstract not provided
Handy, Joseph V.↗
SEARCH · Engineering Papers
Results for “3D battery”
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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A novel shallow bore ground heat exchanger for ground source heat pump applications—Model development and validation
A novel ground heat exchanger design, the Underground Thermal Battery (UTB), was proposed as a low-cost alternative to the conventional vertical bore ground heat exchanger (VBGHE) for the application of ground source heat pumps (GSHPs). The UTB is designed to be installed in a shallow borehole (less than 6 m deep) and thus could cost much less than the conventional VBGHE, which usually is installed in vertical bores 60 m deep. By utilizing natural convection of water and phase change materials, the UTB tempers its temperature change in response to thermal loads, which helps improve the efficiency of GSHPs. A one-dimensional (1D) model of the UTB has been developed and validated with the measured performance data of a small-scale UTB, as well as the simulation results of a more detailed three dimensional (3D) numerical model, which accounts for both heat transfer and fluid dynamics in the UTB. Further, this 1D model is computationally much more efficient than the 3D model and thus can simulate the annual performance of the UTB with acceptable computation time. The 1D model has been used to evaluate the performance of the UTB so that it can be compared with the conventional VBGHE.
42 ENGINEERING↗
Li 8 MnO 6 : A Novel Cathode Material with Only Anionic Redox
In Li-excess transition-metal-oxide cathode materials, anionic oxygen redox can offer high capacity and high voltages, although peroxo and superoxo species may cause oxygen loss, poor cycling performance, and capacity fading. Previous work showed that undesirable formation of peroxide and superoxide bonds is controlled to some extent by Mn substitution, and the present work uses density functional calculations to examine the reasons for this by studying the anionic redox mechanism Li 8 MnO 6 . This material is obtained by substituting Mn for Sn in Li 8 SnO 6 or for Zr in Li 8 ZrO 6 , and we also compare to previous work on those materials. The calculations predict that Li 8 MnO 6 is stable at room temperature (with a band gap of 3.19 eV as calculated HSE06 and 1.82 eV as calculated with the less reliable with PBE+U), and they elucidate the chemical and structural effects involved in the inhibition of oxygen release in this cathode. Throughout the whole delithiation process, only O 2- ions are oxidized. The directional Mn-O bonds formed from unfilled 3d orbitals effectively inhibit the formation of O-O bonds, and the layered structure is maintained even after removing 3 Li per Li 8 MnO 6 formula unit. The calculated average voltage for removal of 3 Li is 3.69 V by HSE06, and the corresponding capacity is 389 mAh/g. The high voltage of oxygen anionic redox and the high capacity result in a high energy density of 1436 Wh/kg. The Li-ion diffusion barrier for the dominant interlayer diffusion path along the c-axis is 0.57 eV by PBE+U. Finally, these results help us to understand the oxygen redox mechanism in a new lithium-rich Li 8 MnO 6 cathode material and contribute to the design of high-energy-density lithium-ion-battery cathode materials with favorable electrochemical properties based on anionic oxygen redox.
Li8MnO6↗
Insight into the deformation features and capacity loss mechanisms of lithium-ion pouch cells under spherical indentation conditions
Mechanical deformation under extreme conditions is one of the important reasons for the failure of lithium-ion batteries in automotive application. However, the deformation features and component failure of lithium-ion cells to external loading has never been a design consideration. Here, in this study, we conduct spherical indentation tests on a dozen of lithium-ion cells with different capacities under different control mode conditions to investigate their deformation features and capacity loss mechanisms. The experimental results show that, under mechanical deformation conditions, internal faults of cells occur in stages, and energy accumulation and sudden release are two key processes of cell's mechanical failure. The cells' state of charge is the main factor affecting their thermal runaway behaviors. In addition, a finite element model is developed to simulate the deformation features and the failure mechanism of key components of lithium-ion pouch cells; the 3D x-ray computed tomography is employed to demonstrate its internal configuration. With this model, the force-strain response, the deformation features as well as the size of the failure area of lithium-ion cells under spherical indentation conditions are accurately predicted. In 3D x-ray computed tomography images, unique mud cracks in cooper current collector are observed, and the influence mechanisms of the isolated fragments on the cell capacities are revealed. These results may provide useful information for the mechanical structure design of the components of lithium-ion pouch cells.
25 ENERGY STORAGE↗
Understanding the Effects of Spaceflight on Head-trunk Coordination during Walking and Obstacle Avoidance
Prolonged exposure to spaceflight conditions results in a battery of physiological changes, some of which contribute to sensorimotor and neurovestibular deficits. Upon return to Earth, functional performance changes are tested using the Functional Task Test (FTT), which includes an obstacle course to observe post‐flight balance and postural stability, specifically during turning. The goal of this study was to quantify changes in movement strategies during turning events by observing the latency between head‐and‐trunk coordinated movements. It was hypothesized that subjects experiencing neurovestibular adaptations would exhibit head‐to‐trunk locking ('en bloc' movement) during turning, exhibited by a decrease in latency between head and trunk movement. FTT data samples were collected from ISS missions. Samples were analyzed three times pre‐exposure, immediately postexposure (1 day post) and 2‐to‐3 times during recovery from the microgravity environment. Two 3D inertial measurements units (XSens MTx) were attached to subjects, one on the head and one on the upper back. This study focused primarily on the yaw movements about the subject's center of rotation. Time differences (latency) between head and trunk movement were calculated at two points on the obstacle course: the first turn to enter the obstacle course (approximately 90⁰ turn) and averaged across a slalom obstacle portion, consisting of three turns (approximately three 90⁰ turns). Preliminary analysis of the data shows a trend toward decreasing head‐to‐trunk movement latency during postflight ambulation in slalom turning after reintroduction to Earth gravity in ISS astronauts. It is clear that changes in movement strategies are adopted during exposure to the microgravity environment and upon reintroduction to a gravity environment. Most ISS subjects exhibit symptoms of neurovestibular changes ('en bloc head and trunk movement) which may impact their ability to perform post‐flight functional tasks.
Madansingh, S.↗
NASA Tech Briefs, June 2003
Topics covered include: Nulling Infrared Radiometer for Measuring Temperature; The Ames Power Monitoring System; Hot Films on Ceramic Substrates for Measuring Skin Friction; Probe Without Moving Parts Measures Flow Angle; Detecting Conductive Liquid Leaking from Nonconductive Pipe; Adaptive Suppression of Noise in Voice Communications; High-Performance Solid-State W-Band Power Amplifiers; Microbatteries for Combinatorial Studies of Conventional Lithium-Ion Batteries; Correcting for Beam Aberrations in a Beam-Waveguide Antenna; Advanced Rainbow Solar Photovoltaic Arrays; Metal Side Reflectors for Trapping Light in QWIPs; Software for Collaborative Engineering of Launch Rockets; Software Assists in Extensive Environmental Auditing; Software Supports Distributed Operations via the Internet; Software Estimates Costs of Testing Rocket Engines; yourSky: Custom Sky-Image Mosaics via the Internet; Software for Managing Inventory of Flight Hardware; Lower-Conductivity Thermal-Barrier Coatings; Process for Smoothing an Si Substrate after Etching of SiO2; Flexible Composite-Material Pressure Vessel; Treatment to Destroy Chlorohydrocarbon Liquids in the Ground; Noncircular Cross Sections Could Enhance Mixing in Sprays; Small, Untethered, Mobile Roots for Inspecting Gas Pipes; Paint-Overspray Catcher; Preparation of Regular Specimens for Atom Probes; Inverse Tomo-Lithography for Making Microscopic 3D Parts; Predicting and Preventing Incipient Flameout in Combustors; MEMS-Based Piezoelectric/Electrostatic Inchworm Actuator; Metallized Capillaries as Probes for Raman Spectroscopy; Adaptation of Mesoscale Weather Models to Local Forecasting; Aerodynamic Design using Neural Networks; Combining Multiple Gyroscope Outputs for Increased Accuracy; and Improved Collision-Detection Method for Robotic Manipulator.
Source record↗
Understanding the Effects of Spaceflight on Head-trunk Coordination during Walking and Obstacle Avoidance
Prolonged exposure to spaceflight conditions results in a battery of physiological changes, some of which contribute to sensorimotor and neurovestibular deficits. Upon return to Earth, functional performance changes are tested using the Functional Task Test (FTT), which includes an obstacle course to observe post‐flight balance and postural stability, specifically during turning. Aims: To quantify changes in movement strategies during turning events by observing the latency between head‐andtrunk coordinated movement. Hypothesis: It is hypothesized that subjects experiencing neurovestibular adaptations will exhibit head‐to‐trunk locking ('en bloc' movement) during turning, exhibited by a decrease in latency between head and trunk movement. Sample: FTT data samples were collected from Shuttle and ISS missions. Samples were analyzed three times pre exposure, immediately post‐exposure (0 or 1 day post) and 2‐to‐3 times during recovery from the microgravity environment. Methods: Two 3D inertial measurements units (XSens MTx) were attached to subjects, one on the head and one on the upper back. This study focused primarily on the yaw movements about the subject's center of rotation. Time differences (latency) between head and trunk movement were calculated at two points: the first turn (Fturn) to enter the obstacle course (approximately 90⁰ turn) and averaged across a slalom obstacle portion, consisting of three turns (approximately three 90⁰ turns). Results: Preliminary analysis of the data shows a trend toward decreasing head‐to‐trunk movement latency during post‐flight ambulation, after reintroduction to Earth gravity in Shuttle and ISS astronauts. Conclusion: It is clear that changes in movement strategies are adopted during exposure to the microgravity environment and upon reintroduction to a gravity environment. Some subjects exhibit symptoms of neurovestibular neuropathy ('en bloc movement') that may impact their ability to perform post‐flight functional tasks.
Madansingh, S.↗
The Dynamical Role of Optical Phonons and Sublattice Screening in a Solid-State Ion Conductor
Solid-state electrolytes (SSEs) require ionic conductivities that are competitive with liquid electrolytes to realize applications in all-solid-state batteries. Although candidate SSEs have been discovered, the underlying mechanisms enabling superionic conduction (>1 mS cm –1 ) remain elusive. In particular, the role of ultrafast lattice dynamics in mediating ion migration, which involves couplings between ions, phonons, and electrons, is rarely explored experimentally at their corresponding time scales. To investigate the complex contributions of coupled lattice dynamics on ion migration, we modulate the charge density occupations within the crystal framework and then measure the time-resolved change in impedance on picosecond time scales for a candidate SSE, Li 0.5 La 0.5 TiO 3 (LLTO). Upon perturbation, we observe enhanced ion migration at ultrafast time scales. The respective transients match the time scales of optical and acoustic phonon vibrations, suggesting their involvement in ion migration. We further computationally evaluate the effect of a charge transfer from the O 2p to the Ti 3d band on the electronic and physical structure of LLTO. We hypothesize that the charge-transfer excitation distorts the TiO 6 polyhedra by altering the local charge density occupancy of the hopping site at the migration pathway saddle point, thereby causing a reduction in the migration barrier for the Li + hop. We rule out the contribution of photogenerated electron carriers and laser heating. Overall, our investigation introduces a new spectroscopic tool to probe fundamental ion hopping mechanisms transiently at ultrafast time scales, which has previously only been achieved in a time-averaged manner or solely via computational methods.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Sub-10 second fly-scan nano-tomography using machine learning
Abstract X-ray computed tomography is a versatile technique for 3D structure characterization. However, conventional reconstruction algorithms require that the sample not change throughout the scan, and the timescale of sample dynamics must be longer than the data acquisition time to fulfill the stable sample requirement. Meanwhile, concerns about X-ray-induced parasite reaction and sample damage have driven research efforts to reduce beam dosage. Here, we report a machine-learning-based image processing method that can significantly reduce data acquisition time and X-ray dose, outperforming conventional approaches like Filtered-Back Projection, maximum-likelihood, and model-based maximum-a-posteriori probability. Applying machine learning, we achieve ultrafast nano-tomography with sub-10 second data acquisition time and sub-50 nm pixel resolution in a transmission X-ray microscope. We apply our algorithm to study dynamic morphology changes in a lithium-ion battery cathode under a heating rate of 50 o C min −1 , revealing crack self-healing during thermal annealing. The proposed method can be applied to various tomography modalities.
36 MATERIALS SCIENCE↗
Activating Single‐Atom Ni Site via First‐Shell Si Modulation Boosts Oxygen Reduction Reaction
Abstract Atomically dispersed nitrogen‐coordinated 3d transition‐metal site on carbon support (M‐NC) are promising alternatives to Pt group metal‐based catalysts toward oxygen reduction reaction (ORR). However, despite the excellent activities of most of M‐NC catalysts, such as Fe‐NC, Co‐NC et al., their durability is far from satisfactory due to Fenton reaction. Herein, this work reports a novel Si‐doped Ni‐NC catalyst (Ni‐SiNC) that possesses high activity and excellent stability. X‐ray absorption fine structure and aberration‐corrected transmission electron microscopy uncover that the single‐atom Ni site is coordinated with one Si atom and three N atoms, constructing Ni‐Si 1 N 3 moiety. The Ni‐SiNC catalyst exhibits a half‐wave potential (E 1/2 ) of 0.866 V versus RHE, with a distinguished long‐term durability in alkaline media of only 10 mV negative shift in E 1/2 after 35 000 cycles, which is also validated in Zn‐air battery. Density functional theory calculations reveal that the Ni‐Si 1 N 3 moiety facilitates ORR kinetics through optimizing the adsorption of intermediates.
Chemistry↗
Sliceable, Moldable, and Highly Conductive Electrolytes for All-Solid-State Batteries
All-solid-state batteries (ASSBs) require solid electrolytes with high ionic conductivity, stability, and deformability for optimal energy and power density. Here, we developed lithium-deficient lithium yttrium bromide (LYB) solid electrolytes, Li 3–x YBr 6–x (0 ≤ x ≤ 0.50), using a comelting method with controlled lithium deficiency. These electrolytes exhibit favorable mechanical properties such as high moldability and sliceability. The Li 2.65 YBr 5.65 composition has an ionic conductivity of 4.49 mS cm –1 at 25 °C and an activation energy of 0.28 eV. Compared to Li 3 YBr 6 , Li 2.65 YBr 5.65 demonstrates improved rate performance and cycling stability in ASSBs. High-resolution X-ray diffraction confirms the formation of the LYB phase with a C2/m space group. Structural analysis reveals increased cation disorder and larger polyhedral volumes for x > 0 in Li 3–x YBr 6–x , contributing to reduced Li + migration energy barriers. Bond valence site energy calculations and molecular dynamics simulations reveal enhanced 3D lithium-ion transport. NMR spectroscopy further highlights increased Li + dynamics and impurity elimination.
Poudel, Tej P. [Florida State Univ., Tallahassee, ↗
Understanding the Effects of Spaceflight on Head-trunk Coordination During Walking and Obstacle Avoidance
Prolonged exposure to spaceflight conditions results in a battery of physiological changes, some of which contribute to sensorimotor and neurovestibular deficits. Upon return to Earth, functional performance changes are tested using the Functional Task Test (FTT), which includes an obstacle course to observe post-flight balance and postural stability, specifically during turning. The goal of this study was to quantify changes in movement strategies during turning events by observing the latency between head-and-trunk coordinated movements. It was hypothesized that subjects experiencing neurovestibular adaptations would exhibit head-to-trunk locking ('en bloc' movement) during turning, exhibited by a decrease in latency between head and trunk movement. FTT data samples were collected from 13 ISS astronauts and 26 male 70-day head down tilt bed rest subjects, including bed rest controls (10 BRC) and bed rest exercisers (16 BRE). Samples were analyzed three times pre-exposure, immediately post-exposure (0 or 1 day post) and 2-to-3 times during recovery from the unloading environment. Two 3D inertial measurements units (XSens MTx) were attached to subjects, one on the head and one on the upper back. This study focused primarily on the yaw movements about the subject's center of rotation. Time differences (latency) between head and trunk movement were averaged across a slalom obstacle portion, consisting of three turns (approximately three 60⁰ turns). All participants were grouped as 'decreaser' or 'increaser,' relating to their change in head-to-trunk movement latency between pre- and post- environmental adaptation measures. Space flight unloading (ISS) showed a bimodal response between the 'increaser' and 'decreaser' group, while both bed rest control (BRC) and bed rest exercise (BRE) populations showed increased preference towards a 'decreaser' categorization, displaying greater head-trunk locking. It is clear that changes in movement strategies are adopted during exposure to an unloading environment. These results further the understanding of vestibular-somatosensory convergence and support the use of bed rest as an exclusionary model to better understand sensorimotor changes in space flight.
Madansingh, S.↗
Assessment of Modeling and Simulation Technical Gaps in Safety Analysis of High Burnup Accident-Tolerant Fuels
The United States nuclear industry is facing a strong challenge to maintain regulatory-required levels of safety while ensuring economic competitiveness to stay in business. Safety remains a key parameter for all aspects related to the operation of light water reactor (LWR) nuclear power plants (NPPs), and it can be achieved more economically by using a risk-informed ecosystem, such as that being developed by the Risk-Informed Systems Analysis (RISA) Pathway under the U.S. Department of Energy (DOE) Light Water Reactor Sustainability (LWRS) Program. The LWRS Program is promoting a wide range of research and development activities to maximize both the safety and economically efficient performance of NPPs through improved scientific understanding, especially given that many plants are considering second license renewal. The RISA Pathway has two main goals: The deployment of methodologies and technologies that enable better representation of safety margins and the factors that contribute to cost and safety, and; The development of advanced applications that enable cost-effective plant operation. As part of the RISA Pathway, the Enhanced Resilient Plant (ERP) project refers to an NPP where safety is improved by implementing various measures, such as accident-tolerant fuels (ATF), diverse and flexible coping strategy (FLEX), enhancements to plant components and systems, incorporation of augmented or new passive cooling systems, and utilization of advanced battery technologies. The objective of the ERP research is to use novel methods and computational tools to enhance existing reactors’ safety while reducing operational costs. Many U.S. utilities are targeting implementation of ATFs instead of traditional fuel in the near future since ATFs offer benefits in terms of improved performance and cost savings. The robust properties of ATF make it possible to extend the refueling cycle from 18 to 24 months in addition to the opportunity to use less of fuel. Extensive safety assessments are required to support regulatory requirements and obtain the approvals to use ATFs and the ERP project support the industry by developing novel effective methodologies for safety evaluations. In this project, the technical gaps in the modeling and simulation of the high burnup (HBU) ATF were assessed in terms of the fuel cladding behavior during the postulated accident events. The issues were identified in modeling the cladding deformation, the hydrodynamic change due to cladding deformation and the critical heat flux (CHF). The RELAP5-3D cladding deformation model was assessed by multiple verification tests and validation with the instrumented fuel assembly (IFA) experiment.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Field Validation of MVA Technology for Offshore CCS: Novel Ultra-High-Resolution 3D Marine Seismic Technology (P-Cable) (Final Report)
The objectives of the proposed study were to deploy and validate a specific monitoring technology, high-resolution 3D marine seismic (HR3D), appropriate for large-demonstration and commercial-scale offshore CCS sites. The project accomplished successful acquisition two HR3D seismic surveys. The first HR3D dataset was over the offshore injection site of the Tomakomai, Japan integrated pilot CCS project, which at the time of survey acquisition was actively injecting CO 2 . The first survey also represented a successful international collaboration between the DOE NETL program and Japan’s national CCS program and was the first successful acquisition and use of HR3D over an active CO 2 injection site (Meckel, Feng et al. 2019). The Tomakomai HR3D survey successfully tested a novel 4-streamer HR3D system array in which, for the first time, no cross-cable (aka “P-Cable”) was utilized and only four GeoEel streamers were used instead of the standard 12-streamer configuration. Consequently, this was not, strictly speaking, a deployment of the “P-Cable” system of (Planke and Berndt 2004) but rather a modified version, thereof, and it is the first known demonstration of the modified system configuration. One very positive outcome from the Japanese collaboration earlier in the project was the ability to learn from the Japanese how they used tail buoys with GPS to determine the position of the seismic source and receivers in time and space. Based on that experience, GCCC designed and built six GPS receivers that could be used to position the streamer receivers and the seismic source via tail buoys. A fundamental advance that was made on the original design, was the ability to directly power the tail buoy GPS units and transfer data through the streamers (i.e., vs. the batteries used at Tomakomai). The bulkiness of the GPS batteries caused drag and episodic surging of the buoys, which affected data quality by lifting up the tail end of the streamers so the receivers were not at the same depth. The units were tested onshore for accuracy and functionality, and the design was subsequently and successfully tested in marine acquisition mode during the SLP survey acquisition. The marine acquisition test and survey satisfied Subtasks 2.2.2, Novel Positioning Technology Selection and Subtask 2.2.3, Novel Positioning Technology Deployment. Results of the novel positioning technology selection (Subtask 2.2.2) were considered successful and will be incorporated in future HR3D seismic acquisition projects to reduce costs, improve deployment safety at sea, and integrate both seismic and data recording via a single data transfer through the streamers to the recording system. The project also established a permitting process through NETL NEPA compliance, which included an Environmental Assessment in a marine setting and is required for conducting these types of surveys using Federal funding. The permitting process charted a “boilerplate,” which can allow future surveys related to other funded projects to move forward more expeditiously. Future improvements that could be considered are more robust seals on the GPS module and stronger materials (especially joints) on tail buoy fabrication. These would increase fixed costs, but would be advisable and probably more economic long-term if multiple HR3D surveys are planned. Project Accomplishments include: • Pre-survey Sensitivity Study • Marine geochemistry methods and data analysis • Successful HR3D seismic dataset acquired @ Tomakomai active CO 2 injection marine site • Developed advanced seismic processing techniques • No NRMS anomalies detected in overburden; Demonstration of containment • Repeatability study • Second survey collected @ San Luis Pass, TX • 4D application using positioning techniques developed in the project for monitoring were successful
3D seismic GPS positioning↗
NASA Tech Briefs, Februrary 2013
Topics covered include: Measurements of Ultra-Stable Oscillator (USO) Allan Deviations in Space; Gaseous Nitrogen Orifice Mass Flow Calculator; Validation of Proposed Metrics for Two-Body Abrasion Scratch Test Analysis Standards; Rover Low Gain Antenna Qualification for Deep Space Thermal Environments; Automated, Ultra-Sterile Solid Sample Handling and Analysis on a Chip; Measuring and Estimating Normalized Contrast in Infrared Flash Thermography; Spectrally and Radiometrically Stable, Wideband, Onboard Calibration Source; High-Reliability Waveguide Vacuum/Pressure Window; Methods of Fabricating Scintillators With Radioisotopes for Beta Battery Applications; Magnetic Shield for Adiabatic Demagnetization Refrigerators (ADR); CMOS-Compatible SOI MESFETS for Radiation-Hardened DC-to-DC Converters; Silicon Heat Pipe Array; Adaptive Phase Delay Generator; High-Temperature, Lightweight, Self-Healing Ceramic Composites for Aircraft Engine Applications; Treatment to Control Adhesion of Silicone-Based Elastomers; High-Temperature Adhesives for Thermally Stable Aero-Assist Technologies; Rockballer Sample Acquisition Tool; Rock Gripper for Sampling, Mobility, Anchoring, and Manipulation; Advanced Magnetic Materials Methods and Numerical Models for Fluidization in Microgravity and Hypogravity; Data Transfer for Multiple Sensor Networks Over a Broad Temperature Range; Using Combustion Synthesis to Reinforce Berms and Other Regolith Structures; Visible-Infrared Hyperspectral Image Projector; Three-Axis Attitude Estimation With a High-Bandwidth Angular Rate Sensor Change_Detection.m; AGATE: Adversarial Game Analysis for Tactical Evaluation; Ionospheric Simulation System for Satellite Observations and Global Assimilative; Modeling Experiments (ISOGAME); An Extensible, User- Modifiable Framework for Planning Activities; Mission Operations Center (MOC) - Precipitation Processing System (PPS) Interface Software System (MPISS); Automated 3D Damaged Cavity Model Builder for Lower Surface Acreage Tile on Orbiter; Mixed Linear/Square-Root Encoded Single-Slope Ramp Provides Low-Noise ADC with High Linearity for Focal Plane Arrays; RUSHMAPS: Real-Time Uploadable Spherical Harmonic Moment Analysis for Particle Spectrometers; Powered Descent Guidance with General Thrust-Pointing Constraints; X-Ray Detection and Processing Models for Spacecraft Navigation and Timing; and Extreme Ionizing-Radiation-Resistant Bacterium
Source record↗
Influence of Potassium Metal-Support Interactions on Dendrite Growth
We report combined synchrotron X-ray nanotomography imaging, cryogenic electron microscopy (cryo-EM) and modeling elucidate how potassium (K) metal-support energetics influence electrodeposit microstructure. Three model supports are employed: O-functionalized carbon cloth (potassiophilic, fully-wetted), non-functionalized cloth and Cu foil (potassiophobic, nonwetted). Nanotomography and focused ion beam (cryo-FIB) cross-sections yield complementary three-dimensional (3D) maps of cycled electrodeposits. Electrodeposit on potassiophobic support is a triphasic sponge, with fibrous dendrites covered by solid electrolyte interphase (SEI) and interspersed with nanopores (sub-10 nm to 100 nm scale). Lage cracks and voids are also a key feature. On potassiophilic support, the deposit is dense and pore-free, with uniform surface and SEI morphology. Mesoscale modeling captures the critical role of substrate-metal interaction on K metal film nucleation and growth, as well as the associated stress state.
36 MATERIALS SCIENCE↗
Descriptor-Based Analysis of Atomic Layer Deposition Mechanisms on Spinel LiMn 2 O 4 Lithium-Ion Battery Cathodes
Protective coatings have been shown to effectively suppress Mn ion dissolution from the spinel LiMn 2 O 4 lithium-ion battery cathode by stabilizing the surface against undesired side reactions with the electrolyte. In spite of extensive study, however, there remains a lack of atomic-scale understanding of how such coatings are deposited, and no molecular-level descriptor to predict trends in deposition mechanisms has been identified. We have recently shown that Al 2 O 3 coatings grown by atomic layer deposition (ALD) with alternating trimethylaluminum (TMA) and water exposures exhibit submonolayer growth because of precursor decomposition on the lithium manganate spinel (LMO) surface during early ALD pulses. In the present work, we elucidate the underlying mechanisms of this Al 2 O 3 ALD process using density functional theory (DFT) calculations and X-ray photoelectron spectroscopy (XPS) experiments, and we introduce a generalized descriptor-based framework to understand the resulting trends across a spectrum of surface structures and functionalities. We demonstrate that all decomposition products, including CH 3 -aluminum adducts and dissociated CH 3 groups, are Lewis bases and are coordinated to oxygen atoms on the LMO surface, leading to charge transfer to Lewis acidic Mn 3d states. Inert-transfer XPS supports these theoretical predictions, showing an increase in near-surface Mn 3+ content following TMA exposure and shifts in C is spectra consistent with C-O bond formation. We extend the DFT studies to various low- and high-index LMO surface facets, as a proxy for tuning the Lewis acid-base interactions between surface-bound CH 3 * and near-surface Mn ions. The thermochemistry for TMA reactions on these chemically distinct LMO surfaces demonstrates that ALD is structure-sensitive and that there is higher reactivity for TMA decomposition and Al 2 O 3 nucleation near LMO steps and defects. Motivated by the Lewis basic character of the decomposition products, we introduce the oxygen vacancy formation energy as a descriptor for decomposition energetics, and we demonstrate that all energetics are correlated to this quantity through the number of electrons that are transferred along the reaction coordinate. Finally, based on these findings, we hypothesize that improved electrochemical cycling with only 1-2 ALD cycles may be due to selective passivation of defect sites on the LMO surface that are more susceptible to Mn dissolution, and we suggest that similar descriptor-based analyses could be useful for the study of other ALD coatings on oxide substrates.
25 ENERGY STORAGE↗
First-principles comparative study of Cr migration in O3 and O/P hybrid-phased NaCrO 2
In layered Na transition-metal (TM) oxides, TM migration usually occurs at highly charged states and severely deteriorates the capacity and reversibility. Meanwhile, the formation of hybrid phases with the intergrowth of octahedral (O-type) and prismatic (P-type) Na layers also takes place at highly charged states. These hybrid phases are often more stable than simple O3 or P3 stackings. However, little is known about the mechanism and impact of TM migration in these hybrid phases. In this work, a comparative first-principles study is performed to understand the connections between structural changes and Cr migration in layered O3 and hybrid-phased NaCrO 2 . After Cr migration, the hybrid-phased NaCrO 2 suffers from greater layer shrinkage than the O3 phase. Three factors affect the Cr migration energy E mig : the Na concentration, local 3D configurations, and 2D in-plane geometries. Low Na concentrations and certain local 3D configurations facilitate the Cr migration. The Cr migration barriers in both O3 and hybrid-phased NaCrO 2 are positively correlated with the Cr E mig . The Cr migration in 17 doped O3 and hybrid-phased NaCrO 2 is surveyed. In these doped NaCrO 2 , a more uniform distribution of the Cr–O bond lengths usually suggests suppressed Cr migration. Optimal dopants for suppressing Cr migration are identified by considering E mig for both Cr and the dopant. Finally, our comparative study on Cr migration in O3 and hybrid-phased NaCrO 2 reveals the significant role of hybrid-phased structures in the development of layered cathode materials.
36 MATERIALS SCIENCE↗