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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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Metastable Li 1+δ Mn 2 O 4 (0 ≤ δ ≤ 1) Spinel Phases Revealed by in Operando Neutron Diffraction and First-Principles Calculations

Here, we examine the reaction mechanisms driven by the lithiation of Li 1+δ Mn 2 O 4 (0 ≤ δ ≤ 1) spinels via in operando neutron powder diffraction (NPD). New reaction mechanisms are proposed involving solid-solution regions within both cubic and tetragonal spinel phases in addition to a continuous phase transition between them. In operando NPD is an ideal tool to follow the light elements such as lithium and oxygen in cathode materials which are often the key to fully understand their structural evolutions. Here, we report a novel methodology to prepare an extremely thick electrode with ~378 mg·cm –2 loading density suitable for the in operando NPD studies. Enabled by such thick electrode, we find that the metal oxygen M–O (M = Li and Mn) bond lengths in both end members LiMn 2 O 4 and Li 2 Mn 2 O 4 experience pronounced changes larger than dictated by the change in lattice parameters because of the locally formed Jahn–Teller distorted Mn 3+ . First-principles density functional theory calculations confirm these metastable intermediates and further propose atomistic reaction pathways for the phase transition by coupling a global structure search algorithm. In conclusion, these findings redefine the conventional understandings on two-phase reactions of this spinel material.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Sulfurized Polyacrylonitrile for High-Performance Lithium–Sulfur Batteries: In-Depth Computational Approach Revealing Multiple Sulfur’s Reduction Pathways and Hidden Li + Storage Mechanisms for Extra Discharge Capacity

Like no other sulfur host material, polyacrylonitrile-derived sulfurized carbon (SPAN) promises improved electrochemical performance for lithium–sulfur batteries, based on its compatibility with carbonate solvents and ability to prevent self-discharge and shuttle effect. However, a complete understanding of the SPAN’s lithiation mechanism is still missing because its structural features vary widely with synthesis conditions, and its electrochemical performance deviates from elemental sulfur. This study continues our research on the elucidation of the SPAN’s structural characteristics and lithiation mechanisms via computational approaches. Here, our models reproduce most experimental data regarding carbon’s graphitization level and conjugated ordering, sulfur–carbon covalent bonding, sulfur loading, and elemental composition. Our simulations emulate the discharge voltage observed in experiments for the first discharge, which reveals that sulfur follows multiple reduction pathways based on its interaction with the carbon backbone. Sulfur reduction takes place above 1.0 V vs Li/Li + mostly in the SPAN-like material, with no long-chain lithium polysulfide formation. Below 1.0 V vs Li/Li + , the backbone’s electrochemical activity occurs via multiple C–Li and N–Li interactions, mostly with edge carbon atoms and pyridinic nitrogen. Moreover, we identify Li + binding sites throughout the graphitized backbone that might lead to prohibited energy costs for Li + deintercalation, which may explain the irreversible capacity loss between the first and second discharges. This work improves understanding of lithiation mechanisms in sulfurized carbon, which is useful for rationally designing SPAN synthesis pathways tailored to increase sulfur loading and enhanced electrochemical performance.

25 ENERGY STORAGE↗
DOE OSTI2019

Modeling Variable-Impedance, Magnetically Insulated, Transmission Lines

Coupling generator current to electron-beam loads and dynamic-inductance loads (z pinches) is greatly improved with low-inductance vacuum transmission lines. Typically, magnetically insulated transmission lines (MITLs) utilize nearly constant impedance geometries where the minimum impedance (anode-cathode gap) is limited by electron loss during the setup of magnetic insulation. Constant-impedance MITL designs are not optimized for low inductance (Zτ) when given a constraint on vacuum electron flow. We describe the design and the modeling of MITLs that have a nonconstant impedance. The baseline variable-impedance MITL designs are based on equilibrium vacuum-electron flow models [1] that are incorporated into the Screamer circuit code [2]. Such designs satisfy the MITL limits in the areal density of the loss current and have magnetically insulated flow that is stable everywhere along the MITL. Different MITL designs are then modeled analytically and with a 2-D particle-in-cell computer code in order to quantify subtle electron losses driven by changes to the vacuum impedance as a function of distance along the transmission line. We present a variable-impedance MITL design that delivers more current with a lower inductance than found in constant-impedance MITL designs.

47 OTHER INSTRUMENTATION↗
DOE OSTI2025

Operando FTIR investigation of salt dynamics in Li-ion batteries during fast charging

Li-ion batteries, when charged at fast-charging rates ($>$2C), suffer from reduced lifetimes and can undergo catastrophic failure. During high-rate charging, Li-ions are unable to rapidly transport through high-loading electrodes ($>$4 mAh cm −2 ). This results in unequal charge distributions, potentials, and utilization of the active material, which can lead to Li plating. Li-ion concentration polarization, in which Li-ions deplete in the anode and accumulate in the cathode during charging, precedes Li plating. An operando FTIR-ATR graphite/NMC cell developed in this research captured Li-ion concentration polarization in real-time. During fast charging, decreases in Li-ion concentration ($>$95%) were measured at the back of the anode. This is the first verification of complete Li-ion depletion within the anode at high C-rates. The measurements also showed graphite stage transition. A P2D model was developed for comparison to the operando measurements. The measurements agreed with the model in some cases, but disparities existed at high C-rates and loadings. In the experiment, the Li-ion concentration often failed to recover to 1.2 M until several hours after charging, whereas the model Li-ion concentration rapidly recovered. The contrast between the model and experiment results indicates that further investigation is required to improve understanding of Li-ion concentration dynamics during fast charging.

25 - ENERGY STORAGE↗
DOE OSTI2021

Load following power generation and power storage using REP and PEM technology

A hydrogen generation system for generating hydrogen and electrical power includes a power supply, a reformer-electrolyzer-purifier (REP) assembly including at least one fuel cell including an anode and a cathode separated by an electrolyte matrix, at least one low temperature fuel cell, and a hydrogen storage. The at least one fuel cell is configured to receive a reverse voltage supplied by the power supply and generate hydrogen-containing gas in the anode of the at least one fuel cell. The at least one low temperature fuel cell is configured to receive the hydrogen-containing gas output from the REP assembly. The at least one low temperature fuel cell is configured to selectably operate in a power generation mode in which the hydrogen-containing gas is used to generate electrical power and a power storage mode in which the hydrogen-containing gas is pressurized and stored in the hydrogen storage.

Jahnke, Fred C.↗
DOE OSTI2020

Modeling Extreme Deformations in Lithium Ion Batteries

A simultaneously coupled modeling approach to study the electrochemical and thermal behavior of lithium-ion batteries under large mechanical deformation has been developed. The thermo-electrochemical pseudo-2D (P2D) battery model is coupled with a mechanical material model. Mechanical, thermal, and electrochemical models are implemented as user-defined sub-routines in the commercial multi-physics code LS-DYNA. The mechanical strain experienced by anode, cathode and separator results in thickness and porosity changes in each layer which in turn influences electrochemical behavior. The evolution of concentration profiles and cell potential are studied under different mechanical loading conditions. Internal short-circuits caused by mechanical deformation and corresponding physical behaviors are also elucidated. We discuss the competing effects of improved transport at higher temperature due to the internal short-circuit versus a drop in the effective ionic conductivity and electrolyte diffusivity due to mechanical deformation.

47 OTHER INSTRUMENTATION↗
NASA NTRS1984

Preparation and evaluation of advanced catalysts for phosphoric acid fuel cells

The platinum electrocatalysts were characterized for their crystallite sizes and the degree of dispersion on the carbon supports. One application of these electrocatalysts was for anodic oxidation of hydrogen in hot phosphoric acid fuel cells, coupled with the influence of low concentrations of carbon monoxide in the fuel gas stream. In a similar way, these platinum on carbon electrocatalysts were evaluated for oxygen reduction in hot phosphoric acid. Binary noble metal alloys were prepared for anodic oxidation of hydrogen and noble metal-refractory metal mixtures were prepared for oxygen reduction. An exemplar alloy of platinum and palladium (50/50 atom %) was discovered for anodic oxidation of hydrogen in the presence of carbon monoxide, and patent disclosures were submitted. For the cathode, platinum-vanadium alloys were prepared showing improved performance over pure platinum. Preliminary experiments on electrocatalyst utilization in electrode structures showed low utilization of the noble metal when the electrocatalyst loading exceeded one weight percent on the carbon.

Stonehart, P.↗
DOE OSTI2019

Silver-Intermediated Perovskite La 0.9 FeO 3–δ toward High-Performance Cathode Catalysts for Nonaqueous Lithium–Oxygen Batteries

Development of efficient cathode catalysts is crucial for achieving high-performance rechargeable lithium–oxygen batteries. Herein, a simple one-step electrospun method was applied to obtain a silver-modified perovskite La 0.9 FeO 3–δ (Ag@LFO) as an efficient cathode catalyst. The synthesized catalyst has two characteristics: first, the doping of Ag led to a tailored electronic structure including the generation of Fe 4+ ; second, the in situ grown Ag exhibits a stronger interaction with perovskite. These two advantages result in high oxygen adsorbability and increased percentage of highly active oxygen species. Furthermore, film-like Li 2 O 2 was observed during discharge on the Ag@LFO cathode, which is beneficial for decomposition during recharge, whereas Li 2 O 2 generated on the LFO cathode was largely toroidal. Density functional theory calculations were used to discuss the Li 2 O 2 growth mechanism. As a result, compared to La 0.9 FeO 3–δ and post-loading silver-decorated La 0.9 FeO 3–δ (Ag/LFO), Ag@LFO exhibits lower overpotential, improved rate-capability, higher discharge specific capacity, and especially promoted cycling performance that is triple that of LFO.

25 ENERGY STORAGE↗
DOE OSTI2024

A thermal evaporation–trapping strategy to synthesize flexible and robust oxygen electrocatalysts for rechargeable zinc–air batteries

Great efforts have been devoted to the development of bifunctional electrocatalysts to accelerate the sluggish kinetics of cathodic oxygen reduction/evolution reactions (ORR/OER) in zinc–air batteries (ZABs). Here we report a thermal evaporation–trapping synergistic strategy to fabricate a bifunctional electrocatalyst of flexible N-doped carbon fiber cloth loaded with both CoFe-oxide nanoparticles and single-atom Co/Fe–Nx sites, in which the thermal evaporation process functions in both downsizing CoFe-oxide nanoparticles and trapping the evaporated Co/Fe species to generate Co/Fe–Nx sites. The obtained flexible electrocatalyst, directly serving as an oxygen electrode, displays a small potential gap of 0.542 V for the OER/ORR, large peak power densities (liquid-state ZAB: 237.4 mW cm2 ; solid-state ZAB: 141.1 mW cm2 ), and excellent charge–discharge cycling stability without decay after working more than 770 hours. Furthermore, in situ Raman spectroscopy characterization and theoretical calculations reveal that CoFe2O4 species is responsible for the OER while atomic Fe/Co sites play a key role in the ORR

Zhang, Hong-Bo↗
DOE OSTI2019

Cooling Induced Surface Reconstruction during Synthesis of High-Ni Layered Oxides

Transition metal layered oxides have been the dominant cathodes in lithium-ion batteries, and among them, high-Ni ones (LiNi x Mn y Co z O 2 ; x ≥ 0.7) with greatly boosted capacity and reduced cost are of particular interest for large-scale applications. The high Ni loading, on the other hand, raises the concern of surface instability and poor rate performance. The rational design of synthesis leading to layered LiNi 0.7 Mn 0.15 Co 0.15 O 2 with greatly enhanced rate capability is reflected, by implementing a quenching process alternative to the general slow cooling. In situ synchrotron X-ray diffraction, coupled with surface analysis, is applied to studies of the synthesis process, revealing cooling-induced surface reconstruction involving Li 2 CO 3 accumulation, formation of a Li-deficient layer and Ni reduction at the particle surface. The reconstruction process happens predominantly at high temperatures (above 350 °C) and is highly cooling-rate dependent, implying that surface reconstruction can be suppressed through synthetic control, i.e., quenching to improve the surface stability and rate performance of the synthesized materials. These findings may provide guidance to rational synthesis of high-Ni cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2020

Corrosion Mitigation and Increased Discharge Capacity in Aqueous Processed Thick Cathodes using Phosphoric Acid Additives

Aqueous processed cathodes for lithium-ion batteries are favorable for both cost and environmental reasons; however, these electrodes still face significant problems with increasing areal capacities (i.e. thickness). Highly basic slurry conditions (pH in excess of 12) corrode the current collector surface and evolve hydrogen gas. Consequently, bubbling at the electrode interface causes substantial damage to the dried electrode. As the loading of these electrodes is increased, damage becomes severe and results in lack of adhesion and cohesion. Here introduction of phosphoric acid to combat the rise in pH and suppress the corrosion at the current collector surface is investigated. Phosphoric acid was added in increments of 0.5, 1.0, and 1.5 wt% and the subsequent effects on slurry rheology, particle size, adhesion, and electrochemical cycling were investigated. A technique is reported for obtaining thick (6-8 mAh/cm2) cathodes that exhibit reduced surface cracking and improved rate performance as compared to control samples.

Kukay, Alexander↗
DOE OSTI2023

Understanding and Mitigating the Dissolution and Delamination Issues Encountered with High-Voltage LiNi 0.5 Mn 1.5 O 4

In our initial study on the high-voltage 5 V cobalt-free spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) cathode, we discovered a severe delamination issue in the laminates when cycled at a high upper cut-off voltage (UCV) of 4.95 V, especially when a large cell format was used. This delamination problem prompted us to investigate further by studying the transition metal (TM) dissolution mechanism of cobalt-free LNMO cathodes, and as a comparison, some cobalt-containing lithium nickel manganese cobalt oxides (NMC) cathodes, as the leachates from the soaking experiment might be the culprit for the delamination. Unlike other previous reports, we are interested in the intrinsic stability of the cathode in the presence of a baseline Gen2 electrolyte consisting of 1.2 M of LiPF 6 in ethylene carbonate/ethyl methyl carbonate (EC/EMC), similar to a storage condition. The electrode laminates (transition metal oxides, transition metal oxides, TMOs, coated on an Al current collector with a loading level of around 2.5 mAh/cm 2 ) or the TMO powders (pure commercial quality spinel LNMO, NMC, etc.) were stored in the baseline solution, and the transition metal dissolution was studied through nuclear magnetic resonance, such as 1 H NMR, 19 F NMR, scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometry (ICP-MS). Significant electrolyte decomposition was observed and could be the cause that leads to the TM dissolution of LNMO. To address this TM dissolution, additives were introduced into the baseline electrolyte, effectively alleviating the issue of TM dissolution. The results suggest that the observed delamination is caused by electrolyte decompositions that lead to etching, and additives such as lithium difluorooxalato borate and p-toluenesulfonyl isocyanate can alleviate this issue by forming a firm cathode electrolyte interface. This study provides a new perspective on cell degradation induced by electrode/electrolyte interactions under storage conditions.

25 ENERGY STORAGE↗
NASA NTRS1995

Ni/NiCI(2) Reference Electrodes For Na/NiCI(2) Cells

Reference electrodes made of nickel cores with surface layers of nickel chloride proposed for use in molten sodium tetracholoroaluminate electrolytes in experimental sodium/nickel chloride electrochemical cells. These and other sodium/metal chloride cells investigated for use in several applications, including powering electric vehicles and leveling loads in power-distribution systems. Offers potential advantages of greater durability, greater stability and reproducibility of electrochemical potentials, less sensitivity of electrochemical potentials to variations in compositions of electrolytes, and greater compatibility with cathodes, made of nickel chloride.

Bugga, Ratnakumar↗
NASA NTRS2003

Phenomenological Model of Current Sheet Canting in Pulsed Electromagnetic Accelerators

The phenomenon of current sheet canting in pulsed electromagnetic accelerators is the departure of the plasma sheet (that carries the current) from a plane that is perpendicular to the electrodes to one that is skewed, or tipped. Review of pulsed electromagnetic accelerator literature reveals that current sheet canting is a ubiquitous phenomenon - occurring in all of the standard accelerator geometries. Developing an understanding of current sheet canting is important because it can detract from the propellant sweeping capabilities of current sheets and, hence, negatively impact the overall efficiency of pulsed electromagnetic accelerators. In the present study, it is postulated that depletion of plasma near the anode, which results from axial density gradient induced diamagnetic drift, occurs during the early stages of the discharge, creating a density gradient normal to the anode, with a characteristic length on the order of the ion skin depth. Rapid penetration of the magnetic field through this region ensues, due to the Hall effect, leading to a canted current front ahead of the initial current conduction channel. In this model, once the current sheet reaches appreciable speeds, entrainment of stationary propellant replenishes plasma in the anode region, inhibiting further Hall-convective transport of the magnetic field; however, the previously established tilted current sheet remains at a fairly constant canting angle for the remainder of the discharge cycle, exerting a transverse J x B force which drives plasma toward the cathode and accumulates it there. This proposed sequence of events has been incorporated into a phenomenological model. The model predicts that canting can be reduced by using low atomic mass propellants with high propellant loading number density; the model results are shown to give qualitative agreement with experimentally measured canting angle mass dependence trends.

Markusic, Thomas↗
DOE OSTI2024

Transforming nanoscale VO 2 (B) into a scalable sodium-ion electrode

The intermittent nature of renewable energies requires highly reliable grid-level energy storage approaches. A critical consideration in developing this technology is the areal capacity which determines battery performance and influences the cost of battery technology. Of related importance is finding new ways of developing scalable electrodes. In recent years, three-dimensional (3D) printing of conductive scaffolds has emerged as an alternative to overcome the scalability limitations of commercial tape cast electrodes. The research carried out in the current study demonstrates a successful scalability pathway for nanoscale VO 2 (B), a desirable cathode for sodium-ion batteries which has a nano-flower morphology with a crystallite size < 20 nm. By electrodepositing VO 2 (B) onto a graphene aerogel scaffold, we were able to achieve mass loading of over 100 mg·cm −2 and still possess an areal capacity of 10 mAh·cm −2 at a current density of 5 mA·cm −2 . Moreover, after 1000 cycles, these electrodes retained 75% to 80% of their initial capacity. Even at high loading levels, the electrodeposited VO 2 (B) exhibits pseudocapacitive material signatures such as a box-like voltammetry response, linear galvanostatic response, and no phase change upon lithiation. The scalability of the VO 2 (B) electrode is demonstrated in a series of experiments which show the areal capacity to scale upon increase in both mass loading and electrode thickness, with only small changes in specific capacity. Furthermore, this study establishes that nanoscale materials can be scaled up to achieve thick electrodes without compromising their electrochemical properties.

additive manufacturing↗
DOE OSTI2021

Slot-die-coating operability windows for polymer electrolyte membrane fuel cell cathode catalyst layers

Roll-to-roll (R2R) slot-die coating of polymer electrolyte membrane fuel cell (PEMFC) catalyst layers represents a scalable deposition method for producing 10–20 m 2 ·min -1 of catalyst-coated gas diffusion layers (GDLs). This high-throughput production technique will help lower the cost of PEMFC catalyst layers. The uniformity of the wet layer applied by slot die deposition is affected by process parameters such as substrate speed, vacuum pressure applied at the upstream meniscus, gap between the slot die lips and substrate, ink rheology, and other ink and substrate properties. The set of conditions for producing a defect-free coating with a dilute ink typically requires little to no upstream vacuum pressure, so suitable operating conditions can be found easily through trial and error and operator intuition. However, the higher viscosity of more concentrated inks dramatically shifts the range of settings that result in a homogeneous coating to higher vacuum levels, which are harder to find through hit or miss. A predictive model showing the range of operable conditions decreases material wastage inherent in experimentally searching for suitable parameters. In this study, the defect-free coating parameter window is explored experimentally and theoretically for two concentrations of PEFC cathode inks. Both a full capillary hydrodynamic model and a computationally cheaper viscocapillary model successfully predict the experimentally determined coating window within the experimental and model uncertainty limits for inks with 5.3 wt% and 12.0 wt% solids ink while maintaining the 0.1 mg Pt ·cm -2 Pt areal loading target. Here, this paper demonstrates a viable pathway for meeting the $30/kW net ultimate cost target of the United States Department of Energy (U.S. DOE) Hydrogen Fuel Cells Technologies Office (HFTO). The concentrated ink lowers the thermal energy and capital expenditure (CapEx) budget of the coating process by decreasing the amount of time, energy, and floorspace required for drying the coating.

25 ENERGY STORAGE↗
NASA NTRS1980

Cockpit displayed traffic information and distributed management in air traffic control

A graphical display of information (such as surrounding aircraft and navigation routes) in the cockpit on a cathode ray tube has been proposed for improving the safety, orderliness, and expeditiousness of the air traffic control system. An investigation of this method at NASA-Ames indicated a large reduction in controller verbal work load without increasing pilot verbal load; the visual work may be increased. The cockpit displayed traffic and navigation information system reduced response delays permitting pilots to maintain their spacing more closely and precisely than when depending entirely on controller-issued radar vectors and speed command.

Kreifeldt, J. G.↗
NASA NTRS1988

Development of the NASA/FLAGRO computer program

A preliminary version of a new computer program has been developed for calculating crack propagation in cyclically loaded structures. The new program, titled NASA/FLAGRO, has numerous enhanced features over previous programs used for safe life analysis on space systems. The essential features of the new program consist of modular design, promptive input using a cathode ray tube terminal, improved crack growth rate analytical methods, many new crack case solutions, and incorporation of user-defined files for material properties and fatigue spectrums. Also, five options made available in the program are to compute: (1) safe life of a part with a preexisting crack; (2) critical crack size for a specified stress level; (3) stress-intensity factor numerical values for making comparisons or checks of solutions; (4) least-squares fit of growth rate equations to crack growth rate data; and (5) the conversion of a versus N data to Delta K versus da/dN.

Forman, Royce G.↗