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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 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Lattice and Local Electronic Structure Modulation Enables Ultra-Long-Life Li-Rich Cathode Materials

Effectively alleviating severe performance deterioration including rapid capacity decay and continuous voltage fading of Li-rich layered oxide (LLO) cathodes by suppressing the irreversible oxygen release and transition metal (TM) migration is a critical challenge during prolonged cycling. Herein, we report a Sb-doped LLO (SLLO) cathode with shortened TM oct –TM oct distance and modulated local electronic structure, which can significantly enhance the oxygen vacancy formation energy and TM migration energy barriers. Therefore, the SLLO cathode showcases an impressive energy density of 1052 Wh kg –1 at 0.2 C and an outstanding rate capability of 214 mAh g –1 at 5 C with a remarkable capacity retention of 79.2% even after 1000 cycles. It should be pointed out that it exhibits greatly enhanced voltage stability with an outstanding voltage retention of 86.2% after cycling 1600 times at 10 C. In conclusion, this work provides a prototype for significantly enhancing the reversibility in electrochemical reactions of high-capacity layered cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2023

Growth of titania and tin oxide from Ti 2 SnC via rapid thermal oxidation in air for lithium-ion battery application

Herein, we report the synthesis of TiO 2 –SnO 2 –C/carbide hybrid electrode materials for Li-ion batteries (LIBs) via two different methods of controlled oxidation of layered Ti 2 SnC. The material was partially oxidized in an open-air furnace (OAF) or using a rapid thermal annealing (RTA) approach to obtain the desired TiO 2 –SnO 2 –C/carbide hybrid material; the carbide phase encompassed both residual Ti 2 SnC and TiC as a reaction product. We tested the oxidized materials as an anode in a half cell to investigate their electrochemical performance in LIBs. Analysis of the various oxidation conditions indicated the highest initial lithiation capacity of 838 mAh/g at 100 mA/g for the sample oxidized in the OAF at 700°C for 1 h. Still, the delithiation capacity dropped to 427 mAh/g and faded over cycling. Long-term cycling demonstrated that the RTA sample treated at 800°C for 30 s was the most efficient, as it demonstrated a reversible capacity of around 270 mAh/g after 150 cycles, as well as a specific capacity of about 150 mAh/g under high cycling rate (2000 mA/g). Given the materials’ promising performance, this processing method could likely be applied to many other members of the MAX family, with a wide range of energy storage applications.

25 ENERGY STORAGE↗
NASA NTRS2017

Methods and Apparatuses for Signaling with Geometric Constellations in a Raleigh Fading Channel

Communication systems are described that use signal constellations, which have unequally spaced (i.e. `geometrically` shaped) points. In many embodiments, the communication systems use specific geometric constellations that are capacity optimized at a specific SNR, over the Raleigh fading channel. In addition, ranges within which the constellation points of a capacity optimized constellation can be perturbed and are still likely to achieve a given percentage of the optimal capacity increase compared to a constellation that maximizes d.sub.min, are also described. Capacity measures that are used in the selection of the location of constellation points include, but are not limited to, parallel decode (PD) capacity and joint capacity.

Barsoum, Maged F.↗
DOE OSTI2021

Ambient Temperature Sodium Polysulfide Catholyte for Nonaqueous Redox Flow Batteries

This study reports a sodium polysulfide catholyte for nonaqueous redox flow batteries (RFBs). We demonstrate reversible capacities up to 200 mAh/gS with negligible fade over 250 cycles at room temperature for sodium polysulfide|biphenyl full cells containing Na + ß '' -Al 2 O 3 solid electrolyte (BASE) membranes. Interestingly, formation of insoluble S and Na 2 S 4 phases did not inhibit the catholyte's cycle life which is likely due to the low concentrations used in the lab-scale prototypes. 3-electrode galvanostatic AC impedance measurements demonstrate that voltage losses were dominated by charge transfer at the cathode, and relevant kinetic parameters (i.e., transfer coefficients and exchange current density) were calculated through a Tafel analysis. To the best of our knowledge, this is the first report applying such an impedance approach to nonaqueous RFBs. Overall, the use of low-cost active materials makes sodium polysulfide|biphenyl RFBs promising for long duration energy storage applications. Furthermore, if strategies are developed to increase the solubility of S and/or low order polysulfides (Na 2 S x , x ≤ 4), specific energies up to 100 Wh kg -1 (including combined mass of the anolyte and catholyte) can be achieved.

25 ENERGY STORAGE↗
DOE OSTI2022

Porosity Development at Li-Rich Layered Cathodes in All-Solid-State Battery during In Situ Delithiation

Structural evolutions are crucial for determining the performance of high-voltage lithium, manganese-rich layered cathodes. Moreover, interface between electrode and electrolyte plays a critical role in governing ionic transfer in all-solid-state batteries. In this work, we unveil two different types of porous structure in Li 1.2 Ni 0.2 Mn 0.6 O 2 cathode with LiPON solid-state electrolyte. Na-nopores are found near the cathode/electrolyte interface at pristine state, where cation mixing, phase transformation, oxygen loss and Mn reduction are also found. In situ Li + extraction induces the evolution of nanovoids, initially formed near the inter-face then propagated into the bulk. Despite the development of nanovoids, layered structure is conserved, suggesting the nature of nanopores and nanovoids are different and their impact would be divergent. This work demonstrates the intrinsic interfacial layer, as well as the dynamic scenario of nanovoid formation inside high-capacity layered cathode, which help understanding the performance fading in cathodes and offer insights into the all-solid-state battery design.

25 ENERGY STORAGE↗
DOE OSTI2024

Cobalt-free composite-structured cathodes with lithium-stoichiometry control for sustainable lithium-ion batteries

Abstract Lithium-ion batteries play a crucial role in decarbonizing transportation and power grids, but their reliance on high-cost, earth-scarce cobalt in the commonly employed high-energy layered Li(NiMnCo)O 2 cathodes raises supply-chain and sustainability concerns. Despite numerous attempts to address this challenge, eliminating Co from Li(NiMnCo)O 2 remains elusive, as doing so detrimentally affects its layering and cycling stability. Here, we report on the rational stoichiometry control in synthesizing Li-deficient composite-structured LiNi 0.95 Mn 0.05 O 2 , comprising intergrown layered and rocksalt phases, which outperforms traditional layered counterparts. Through multiscale-correlated experimental characterization and computational modeling on the calcination process, we unveil the role of Li-deficiency in suppressing the rocksalt-to-layered phase transformation and crystal growth, leading to small-sized composites with the desired low anisotropic lattice expansion/contraction during charging and discharging. As a consequence, Li-deficient LiNi 0.95 Mn 0.05 O 2 delivers 90% first-cycle Coulombic efficiency, 90% capacity retention, and close-to-zero voltage fade for 100 deep cycles, showing its potential as a Co-free cathode for sustainable Li-ion batteries.

36 MATERIALS SCIENCE↗
NASA NTRS1980

Adaptive rain fade compensation

A large available margin must be provided for satellite communications systems operating near 20 GHz, which occasionally experience fades due to rain attenuation. It is proposed that this margin may be achieved in high-capacity FDMA satellites by dynamically providing a large margin to those links which are experiencing deep fades, while maintaining a small fade margin on all others. Single-beam SCPC operation and multiple-beam, satellite-switched FDMA systems are described, and the optimization of the dynamic FDMA links in a severely fading environment is investigated. A solution is derived which takes into account: (1) transponder intermodulation distortion, (2) cochannel and cross-polarization antenna interference, and (3) rain fade characteristics. The sample system configuration presented shows that such systems reach availability levels approaching 0.9999 at Ka-Band.

Rautio, J. C.↗
DOE OSTI2022

The influence of temperature on area-specific impedance and capacity of Li-ion cells with nickel-containing positive electrodes

The temperature-dependent behaviors of five nickel-containing positive electrodes (NCA, NMC811, NMC622, NMC532, and NMC111) in lithium-ion batteries are investigated using an electrochemical protocol involving rate studies, mild aging (~100 cycles), and hybrid pulse power characterization (HPPC). Tests are conducted using coin-cells with graphite negative electrodes at -20 °C, 0 °C, 20 °C, and 40 °C. Three techniques are compared for determining the area-specific impedance (ASI): i) fits to the rate study average voltages, ii) fitting to the entire voltage curves using a regularization scheme, and iii) HPPC. When fit to an Arrhenius-type equation, all methods yield similar apparent activation energies (±2 kJ/mol) for the impedance, which range from -20 to -31 kJ/mol for the electrodes. Impedance growth increases with temperature but remains at less than 0.2% per cycle for most electrodes and temperatures. NCA and NMC811 are the exceptions, which yield 0.5% and 1.5% increases in ASI per cycle, respectively, at 40 °C. For cells with the same electrodes, the capacities are similar at 20 and 40 °C but reduce at lower temperatures, with up to a 52% reduction at -20 °C and 2C. The fade in energy of the cells during C/3 cycling is attributed to decreasing capacity as opposed to increasing ASI.

25 ENERGY STORAGE↗
DOE OSTI2022

Perspective—Potential Benefit of Li-Rich Cathode Materials: Reduction of Co and Ni Content Rather than Achievement of Ultra-High Capacities

In the conventional cycling protocol for lithium and manganese rich NMC layered oxides (LMRNMC), the upper cutoff voltage V cut is extended to ~ 4.8, to achieve capacities of similar to 250 mAh g -1 . With this mode of operation, structural rearrangements result in voltage fade upon cycling. Herein, a strategy is proposed to avoid these structural rearrangements based on (a) restricting V cut to values < ~ 4.6 to shut down the bulk instabilities, and (b) application of a (preferably) semi-coherent coating that protects the surface oxygen. The potential benefit of this strategy would be to minimize Co and Ni content, compared to Ni-rich NMC.

25 ENERGY STORAGE↗
DOE OSTI2020

High Capacity Adsorption—Dominated Potassium and Sodium Ion Storage in Activated Crumpled Graphene

In this study, structurally and chemically defective activated-crumbled graphene (A-CG) is employed to achieve unique synergy of large reversible potassium (K) and sodium (Na) ion storage capacity with fast charging and extended cyclability. A-CG synthesis consists of low temperature spraying of graphene oxide slurry, followed by partial reduction annealing and air activation. For K storage, the reversible capacities are 340 mAh g -1 at 0.04 A g -1 , 261 mAh g -1 at 0.5 A g -1 , and 210 mAh g -1 at 2 A g -1 . For Na storage, the reversible capacities are 280 mAh g -1 at 0.04 A g -1 , 191 mAh g -1 at 0.5 A g -1 , and 151 mAh g -1 at 2 A g -1 . A-CG shows a stable intermediate rate (0.5 Ag -1 ) cycling with both K and Na, with minimal fade after 2800 and 8000 cycles. These are among the most favorable capacity—rate capability—cyclability combinations recorded for potassium-ion battery and sodium-ion battery carbons. Electroanalytical studies (cyclic voltammetry, galvanostatic intermittent titration technique, b -value) and density functional theory (DFT) reveal that enhanced electrochemical performance originates from ion adsorption at various defects, such as Stone–Wales defects. Moreover, DFT highlights enhanced thermodynamic stability of A-CG with adsorbed K versus with adsorbed Na, explaining the unexpected higher reversible capacity with the former.

25 ENERGY STORAGE↗
DOE OSTI2023

Effect of the Nature of Both Cation and Anion Substitution on the Structural Symmetry of Li‐Rich 3 d ‐Metal Chalcogenide Electrodes

Abstract Li‐rich layered chalcogenides have recently led to better understanding of the anionic redox process and its associated high capacity while providing ways to overcome its practical limitations of voltage fade and irreversibility. This study reports on the feasibility of triggering anionic activity in Li 2 TiS 3 , through anionic substitution (Se for S) or cationic substitution (Fe for Ti). Herein, the chalcogenide chemical space is further explored to prepare mono‐substituted Li 1.7 Ti 0.85 Mn 0.45 Ch 3 (Ch = S/Se) and doubly substituted cationic and anionic phases (Li 1.7 Ti 0.85 Fe 0.45 S 3‐z Se z ) which crystallize either in the O3‐ or O1‐type structures depending upon substituents. All series show a bell‐shape capacity variation as function of the transition metal (TM) substitution degree with values up to 240 mAh g −1 . For specific compositions, a structural O3 to O1 phase transition is observed upon Li removal, which is not reversible upon Li re‐insertion due to kinetic limitations and negatively affects long‐term cycling performance. Density functional theory (DFT) calculations confirm the O3/O1 relative stability along the different series and point subtle electronic differences in the TM‐doping, rationalizing the structural and electrochemical behaviors of these phases upon cycling. These findings provide further insights into the link between structural and electronic stability, which is of key importance for designing chalcogenide‐based anionic redox compounds.

Chemistry↗
DOE OSTI2024

Unleashing the Potential of Fast Charging Batteries: Leveraging Anion Redox Chemistry in Ni- and Co-Free Cathodes

Designing Li-ion battery cathodes free from critical raw materials such as Co and Ni has a huge technological and societal impact. Though anion redox-based Li-rich oxide cathodes allow designing Co and Ni free cathode compositions, the Li-rich oxides witnessed voltage fade, voltage hysteresis, and irreversible oxygen release despite their high capacity. Conversely, anion redox through highly covalent chalcogenides (S/Se) is emerging due to the improved covalency between metal d and ligand p bands. Here, we investigate the tuning of multi-chalcogen (S/Se) p-band and redox-active metal d-band in a model Li-rich chalcogen composition Li 1.13 Ti 0.57 Fe 0.3 S 2-y Se y (y = 0 - 1) through in-depth electrochemical, X-ray spectroscopy, and DFT-based electronic structure investigations. Introducing the appropriate amount of Se p band character in anion redox sulfides increases interlayer distance and metal - ligand covalency without modifying the original crystal structure, promoting significant electrochemical reversibility through mixed anionic (Se 2- /Se n- , S 2- /S n- , wherein n<2) and cationic (Fe 2+ /Fe 3+ ) redox reactions. Here we show the detailed Fe, S, and Se redox contributions during Li insertion/extraction through X-ray Absorption (XAS) and Hard X-ray Photoemission Spectroscopy (HAXPES) measurements. The orbital tuning approach improves rate capability for more than 10 C charge-discharge rate, exhibiting more than 50% of its original capacity obtained at C/20 rate. The buffer cation in the lattice (Ti 4+ ) remains electrochemically inactive even after significant Se p-band introduction in the sulfide framework. Overall, this work takes advantage of multi-anion redox chemistry to uncover practically demanding fast charging-discharging characteristics in intercalation cathodes. The obtained knowledge of this design can be extended to other oxide and chalcogen cathodes for high performance Li-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Correlating concerted cations with oxygen redox in rechargeable batteries

Rechargeable batteries currently power much of our world, but with the increased demand for electric vehicles (EVs) capable of traveling hundreds of miles on a single charge, new paradigms are necessary for overcoming the limits of energy density, particularly in rechargeable batteries. The emergence of reversible anionic redox reactions presents a promising direction toward achieving this goal; however this process has both positive and negative effects on battery performance. While it often leads to higher capacity, anionic redox also causes several unfavorable effects such as voltage fade, voltage hysteresis, sluggish kinetics, and oxygen loss. However, the introduction of cations with topological chemistry tendencies has created an efficient pathway for achieving long-term oxygen redox with improved kinetics. The cations serve as pillars in the crystal structure and meanwhile can interact with oxygen in ways that affect the oxygen redox process through their impact on the electronic structure. This review delves into a detailed examination of the fundamental physical and chemical characteristics of oxygen redox and elucidates the crucial role that cations play in this process at the atomic and electronic scales. Furthermore, here we present a systematic summary of polycationic systems, with an emphasis on their electrochemical performance, in order to provide perspectives on the development of next-generation cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2020

Accommodation of Silicon in an Interconnected Copper Network for Robust Li-Ion Storage

Silicon (Si)-based materials are one of the most promising anodes to be applied in rechargeable lithium ion batteries. However, the active Si/electrolyte interface causes continuous side reactions and poor conductivity, which significantly decreases the cycling stability. Cu is the only metallic current collector that has been known to promote electron conduction and lithium-ion transfer without alloying reaction occurrence. However, to the best current knowledge, scalable interface engineering incorporating Cu has not been reported. In this study, this conductive Cu interface (CCI) is constructed through a self-assembly carbothermic reduction method to achieve efficient protection of Si/electrolyte interfaces while allowing for fast Li + diffusion. The energy barrier of lithium-ion diffusion through Cu is calculated to be 0.1965 eV, which is much lower than that through Au, Fe, and Ni films. Benefiting from the enhanced interfacial protection and kinetics of Si with CCI, a fading rate of only 0.068% is maintained for 1000 cycles and an aerial capacity of 4.78 mAh cm -2 is achieved after 280 cycles, which is comparable to the industry standards required for practical application.

36 MATERIALS SCIENCE↗
NASA NTRS2000

T1 VSAT Fade Compensation Statistical Results

New satellite communication systems are steadily seeking to use higher frequency bands to accommodate the requirements for additional capacity. At these higher frequencies, propagation impairments that did not significantly affect the signal at lower frequencies begin to have considerable impact. In Ka-band. the next logical commercial frequency band to be used for satellite communication, attenuation of the signal due to rain is a primary concern. An experimental satellite built by NASA, the Advanced Communication Technology Satellite (ACTS). launched in September 1993, is the first U.S. communication satellite operating in the Ka-band. In addition to higher carrier frequencies, a number of other new technologies, including on-board baseband processing. multiple beam antennas, and rain fade detection and compensation techniques, were designed into the ACTS. Verification experiments have been conducted since the launch to characterize the new technologies. The focus of this paper is to characterize the method used by the ACTS TI Very Small Aperture Terminal (TI VSAT) ground stations in detecting the presence of fade in the communication signal and to adaptively compensate for it by the addition of burst rate reduction and forward error correction. Measured data obtained from the ACTS program was used to validate the compensation technique. A software process was developed and demonstrated to statistically characterize the increased availability achieved by the compensation techniques in terms of the bit error rate time enhancement factor. Several improvements to the ACTS technique are discussed and possible implementations for future Ka band system are offered.

Johnson, Sandra K.↗
DOE OSTI2022

Reconfigurable Intelligent Surfaces Empowered THz Communication in LEO Satellite Networks

Massive swarms of low Earth orbit (LEO) satellites are poising to serve for high-speed and low-latency ubiquitous connectivity with almost global coverage. Broadband inter-satellite communication is one of the key elements of satellite communication systems that orchestrate massive satellite swarms in cooperation. Thanks to technological advancements in microelectronics and micro-systems, the terahertz (THz) band has emerged as a strong candidate for inter-satellite links (ISLs) due to its promise of wideband communication. Especially, multi-antenna systems can improve the system performance along with the wideband supported by the THz band. However, multi-antenna systems should be reconsidered due to their size, weight, and price/power (SWaP) constraints. On the other hand, as a state-of-art multi-antenna technology, reconfigurable intelligent surface (RIS) is able to relax SWaP constraints because of its passive component-based structures. However, as similar reflection characteristic throughout wideband is difficult to meet, it is possible to observe beam misalignment. In this work, we first provide an assessment of the use of the THz band for ISLs and quantify the impact of misalignment fading on error performance. Then, in order to compensate for the high path loss associated with high carrier frequencies, and to further improve the signal-to-noise ratio (SNR), we propose the use of RISs mounted on neighboring satellites to enable signal propagation. Based on a mathematical analysis of the problem, we present the error rate expressions for RIS-assisted ISLs with misalignment fading. Also, numerical results show that RIS can leverage the error rate performance and achievable capacity of THz ISLs.

reconfigurable intelligent surfaces (RISs)↗
DOE OSTI2023

Effect of Si Content on Extreme Fast Charging Behavior in Silicon–Graphite Composite Anodes

Commercial Li-ion batteries typically incorporate a small amount of high-capacity silicon (Si)-based materials in the composite graphite-based anode to increase the energy density of the battery. However, very little is known about the effects of Si on the fast-charging behavior of composite anodes. Herein, we examine the effects of the Si/graphite ratio in the composite anode on the fast-charging behavior of full cells. We show that addition of Si increases the rate capability from 1C to 8C and improves the capacity retention in early cycles at 6C due to reduced overpotential in constant current charging cycles. The impacts of Si content on fast-charging aging were identified by Post-Test characterization. Despite realizing benefits of available capacity and reduced Li plating at 6C, silicon–electrolyte interactions lead the time-dependent cell performance to fade quickly in the long term. The Post-Test analysis also revealed the thickening of the electrode and nonuniform distribution of electrolyte decomposition products on the Si-containing anodes, as well as the organic-rich solid electrolyte interphase (SEI), which are the factors behind cell degradation. Our study sheds insight on the advantages and disadvantages of Si/graphite composite anodes when they are used in fast-charging applications and guides further research in the area by designing an optimized composition of Si incorporated in a mature graphite matrix.

25 ENERGY STORAGE↗
NASA NTRS2001

Analysis of Fade Detection and Compensation Experimental Results in a Ka-Band Satellite System

The frequency bands being used for new satellite communication systems are constantly increasing to accommodate the requirements for additional capacity. At these higher frequencies, propagation impairments that did not significantly affect the signal at lower frequencies begin to have considerable impact. In Ka-band, the next logical commercial frequency band to be used for satellite communication, attenuation of the signal due to rain is a primary concern. An experimental satellite built by NASA, the Advanced Communication Technology Satellite (ACTS), launched in September 1993, is the first US communication satellite operating in the Ka-band. In addition to higher carrier frequencies, a number of other new technologies, including onboard baseband processing, multiple beam antennas, and rain fade detection and compensation techniques, were designed into the ACTS. Verification experiments have been conducted since the launch to characterize the new technologies. The focus of this thesis is to describe and validate the method used by the ACTS Very Small Aperture Terminal (VSAT) ground stations in detecting the presence of fade in the communication signal and to adaptively compensate for it by the addition of burst rate reduction and forward error correction. Measured data obtained from the ACTS program is used to validate the compensation technique. In this thesis, models in MATLAB are developed to statistically characterize the increased availability achieved by the compensation techniques in terms of the bit error rate time enhancement factor. Several improvements to the ACTS technique are discussed and possible implementations for future Ka-band systems are also presented.

Johnson, Sandra↗