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DOE OSTI2024

Impacts of Curing-Induced Phase Segregation in Silicon Nanoparticle-Based Electrodes

We report the investigation of silicon nanoparticle composite anodes for Li-ion batteries, using a combination of two nm-scale atomic force microscopy-based techniques: scanning spreading resistance microscopy for electrical conduction mapping and contact resonance and force volume for elastic modulus mapping, along with scanning electron microscopy-based energy dispersion spectroscopy, nanoindentation, and electrochemical analysis. Thermally curing the composite anode—made of polyethylene oxide-treated Si nanoparticles, carbon black, and polyimide binder—reportedly improves the anode electrochemical performance significantly. This work demonstrates phase segregation resulting from thermal curing, where alternating bands of carbon and silicon active material are observed. This electrode morphology is retained after extensive cycling, where the electrical conduction of the carbon-rich bands remains relatively unchanged, but the mechanical modulus of the bands decreases distinctly. These electrical and mechanical factors may contribute to performance improvement, with carbon bands serving as a mechanical buffer for Si deformation and providing electrical conduction pathways. This work motivates future efforts to engineer similar morphologies for mitigating capacity loss in silicon electrodes.

25 ENERGY STORAGE↗

NASA NTRS2016

Analysis of the Capacity Potential of Current Day and Novel Configurations for New York's John F. Kennedy Airport

In 2015, a series of systems analysis studies were conducted on John F. Kennedy Airport in New York (NY) in a collaborative effort between NASA and the Port Authority of New York and New Jersey (PANYNJ). This work was performed to build a deeper understanding of NY airspace and operations to determine the improvements possible through operational changes with tools currently available, and where new technology is required for additional improvement. The analysis was conducted using tool-based mathematical analyses, video inspection and evaluation using recorded arrival/departure/surface traffic captured by the Aerobahn tool (used by Kennedy Airport for surface metering), and aural data archives available publically through the web to inform the video segments. A discussion of impacts of trajectory and operational choices on capacity is presented, including runway configuration and usage (parallel, converging, crossing, shared, independent, staggered), arrival and departure route characteristics (fix sharing, merges, splits), and how compression of traffic is staged. The authorization in March of 2015 for New York to use reduced spacing under the Federal Aviation Administration (FAA) Wake Turbulence Recategorization (RECAT) also offers significant capacity benefit for New York airports when fully transitioned to the new spacing requirements, and the impact of these changes for New York is discussed. Arrival and departure capacity results are presented for each of the current day Kennedy Airport configurations. While the tools allow many variations of user-selected conditions, the analysis for these studies used arrival-priority, no-winds, additional safety buffer of 5% to the required minimum spacing, and a mix of traffic typical for Kennedy. Two additional "novel" configurations were evaluated. These configurations are of interest to Port Authority and to their airline customers, and are believed to offer near-term capacity benefit with minimal operational and equipage changes. One of these is the addition of an Optimized Profile Descent (OPD) route to runways 22L and 22R, and the other is the simultaneous use of 4 runways, which is not currently done at Kennedy. The background and configuration for each of these is described, and the capacity results are presented along with a discussion of drawbacks and enablers for each.

Glaab, Patricia↗

DOE OSTI2023

Conducting Polymers Meet Lithium–Sulfur Batteries: Progress, Challenges, and Perspectives

Lithium–sulfur (Li–S) batteries have attracted increased interest because of the high theoretical energy density, low cost, and environmental friendliness. Conducting polymers (CPs), as one of the most promising materials used in Li–S batteries, can not only facilitate electron transfer and buffer the large volumetric change of sulfur benefiting from their porous structure and excellent flexibility, but also enable stronger physical/chemical adsorption capacity toward polysulfides (LiPSs) when doped with abundant heteroatoms to promote the sulfur redox kinetics and achieve the high sulfur loading. This review firstly introduces the properties of various CPs including structural CPs (polypyrrole (PPy), polyaniline (PANi), polyethylene dioxothiophene [PEDOT]) and compound CPs (polyethylene oxide (PEO), polyvinyl alcohol (PVA) and poly(acrylic acid) [PAA]), and their application potential in Li–S batteries. Furthermore, the research progress of various CPs in different components (cathode, separator, and interlayer) of Li–S batteries is systematically summarized. Finally, the application perspective of the CPs in Li–S batteries as a potential guidance is comprehensively discussed.

Chen, Xin↗

NASA NTRS1980

REDOX electrochemical energy storage

Reservoirs of chemical solutions can store electrical energy with high efficiency. Reactant solutions are stored outside conversion section where charging and discharging reactions take place. Conversion unit consists of stacks of cells connected together in parallel hydraulically, and in series electrically. Stacks resemble fuel cell batteries. System is 99% ampere-hour efficient, 75% watt hour efficient, and has long projected lifetime. Applications include storage buffering for remote solar or wind power systems, and industrial load leveling. Cost estimates are $325/kW of power requirement plus $51/kWh storage capacity. Mass production would reduce cost by about factor of two.

Thaller, L. H.↗

DOE OSTI2023

High Sulfur Loading and Capacity Retention in Bilayer Garnet Sulfurized‐Polyacrylonitrile/Lithium‐Metal Batteries with Gel Polymer Electrolytes

The cubic‐garnet (Li 7 La 3 Zr 2 O 12 , LLZO) lithium–sulfur battery shows great promise in the pursuit of achieving high energy densities. The sulfur used in the cathodes is abundant, inexpensive, and possesses high specific capacity. In addition, LLZO displays excellent chemical stability with Li metal; however, the instabilities in the sulfur cathode/LLZO interface can lead to performance degradation that limits the development of these batteries. Therefore, it is critical to resolve these interfacial challenges to achieve stable cycling. Here, an innovative gel polymer buffer layer to stabilize the sulfur cathode/LLZO interface is created. Employing a thin bilayer LLZO (dense/porous) architecture as a solid electrolyte and significantly high sulfur loading of 5.2 mg cm −2 , stable cycling is achieved with a high initial discharge capacity of 1542 mAh g −1 (discharge current density of 0.87 mA cm −2 ) and an average discharge capacity of 1218 mAh g −1 (discharge current density of 1.74 mA cm −2 ) with 80% capacity retention over 265 cycles, at room temperature (22 °C) and without applied pressure. Achieving such stability with high sulfur loading is a major step in the development of potentially commercial garnet lithium–sulfur batteries.

25 ENERGY STORAGE↗

DOE OSTI2020

Superlattice-Structured Films by Magnetron Sputtering as New Era Electrodes for Advanced Lithium-ion Batteries

Sustaining sound structures in Si-based anodes is extremely challenging because of the high volumetric expansion that occurs upon cycling. To maintain high capacities over cycles, new designs rely on engineering-specific hierarchical geometries and/or optimized composite compositions such that at least one of the multiple elements serves as buffer and/or electron conductive pathways in the electrodes. In this paper, we report an innovative design in which alternating layers of periodic atomic structures involving multiple elements form a new anode material for lithium-ion batteries. In this work, a superlattice-structured amorphous film made using Si, Mo, and Cu is fabricated by a simple and scalable magnetron sputtering process for the first time. This continuous and repetitive superlattice formation along the film thickness provides a homogeneous stress-strain distribution. The Mo-Cu layer in the superlattice acts as an inactive-conductive layer and as a backbone to handle the volume expansion of active Si upon cycling. This nano-functional superlattice approach enables harnessing the high energy density of Si while maintaining its structural stability. As a result, the electrode exhibits high specific capacity and capacity retention even at high cycling rates. The possible use of the film in a full cell is also evaluated by cycling it vs. the LiMn 1.5 Ni 0.5 O 4 cathode. The full cell maintains a stable capacity of about 900 mAh g anode -1 over 150 cycles, at ~600 mA g -1 rate. The remarkable performance of this nano-functional superlattice film is found to be promising as anodes for applications that require high energy, long calendar life, and excellent abuse tolerance such as electric vehicle batteries.

25 ENERGY STORAGE↗

DOE OSTI2020

Understanding Stabilization in Nanoporous Intermetallic Alloy Anodes for Li-Ion Batteries Using Operando Transmission X-ray Microscopy

Tin-based alloying anodes are exciting due to their high energy density. Unfortunately, these materials pulverize after repetitive cycling due to the large volume expansion during lithiation and delithiation; both nanostructuring and intermetallic formation can help alleviate this structural damage. Here, these ideas are combined in nanoporous antimony–tin (NP-SbSn) powders, synthesized by a simple and scalable selective-etching method. The NP-SbSn exhibits bimodal porosity that facilitates electrolyte diffusion; those void spaces, combined with the presence of two metals that alloy with lithium at different potentials, further provide a buffer against volume change. This stabilizes the structure to give NP-SbSn good cycle life (595 mAh/g after 100 cycles with 93% capacity retention). Operando transmission X-ray microscopy (TXM) showed that during cycling NP-SbSn expands by only 60% in area and then contracts back nearly to its original size with no physical disintegration. The pores shrink during lithiation as the pore walls expand into the pore space and then relax back to their initial size during delithiation with almost no degradation. Importantly, the pores remained open even in the fully lithiated state, and structures are in good physical condition after the 36th cycle. The results of this work should thus be useful for designing nanoscale structures in alloying anodes.

25 ENERGY STORAGE↗

DOE OSTI2024

Value of Nuclear Energy to the Reliability of the North American Power System: Results for Western and Eastern Interconnections

This report documents the fulfillment of a milestone for the United States (U.S.) Department of Energy Office of Nuclear Energy Light Water Reactor Sustainability Program: completing a baseline study of regional impact of nuclear power plants and hydrogen production in maintaining grid services and power quality. Models have been comprehensively demonstrated for the Western Interconnection, or Western Electric Coordinating Council area, and in the Eastern Interconnection for scenarios representative of past extreme events (e.g., drought and heat waves). Understanding the impact on the reliability of the bulk electric system of any reduction in generation capacity from nuclear power, for any reason, is the motivation of this work. Factors that might lead to the premature or unplanned closure of nuclear plants, extended outages, or repurposing of nuclear power include: • Aging infrastructure: Many nuclear power plants in the U.S. are nearing the end of their designed operating lives. Upgrading aging infrastructure can be expensive, and some utilities may choose to retire plants rather than invest in costly upgrades. • Low wholesale electricity prices: The deregulation of the electricity market in many states has led to increased competition and driven down wholesale electricity prices, causing nuclear power operators to seek other revenue sources for their heat and power such as clean hydrogen production. • Renewables growth: The rapid growth of renewable energy sources like solar and wind power is posing a challenge to traditional generation sources like nuclear. While many see renewables as a key part of the clean energy transition, their intermittent nature requires additional grid solutions for reliable power supply. • The potential for regulatory decisions to be in conflict: In its 2021 rulemaking, EPA rule (86 FR 880), the Environmental Protection Agency (EPA) set a compliance date for the ban on processing and distribution in commerce of Decabromodiphenyl Ether (DecaBDE). Since DecaBDE is in many components, particularly wiring, of nuclear power plants which are deemed safety-related or important to safety, three plants would not have been able to restart after their 2023 spring outages, and numerous others would have faced issues in the near future. Fortunately, in this case, the EPA provided relief to the nuclear energy industry. The report provides a summary of the significant role nuclear energy plays in the United States’ power generation mix, supplying around 20% of the nation’s electricity generation, spread across 28 U.S. states. Nuclear power is reliable, mostly unaffected by weather and seasonal changes, and provides a consistent source of baseload power. In terms of capacity, nuclear power plants account for as much as 26% of balancing area power generation capacity. Nuclear power also provides a substantial contribution (e.g., 10% of the inertia in the Eastern Interconnection) of the synchronous spinning mass/inertia that buffers the rate at which frequency changes when a load and generation imbalance occurs (e.g., a large plant trips or a load is suddenly shed due to a transmission outage). This contribution is critical for maintaining grid stability during sudden changes in load or generation.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

NASA NTRS1999

Boronate affinity adsorption of RNA: possible role of conformational changes

Batch equilibrium adsorption isotherm determination is used to characterize the adsorption of mixed yeast RNA on agarose-immobilized m-aminophenylboronic acid. It is shown that the affinity-enhancing influence of divalent cations depends strongly on the precise nature of the cation used, with barium being far more effective than the conventionally-used magnesium. This adsorption-promoting influence of barium is suggested to arise primarily from ionic influences on the structure and rigidity of the RNA molecule, as the adsorption of ribose-based small molecules is not similarly affected. The substitution of barium for the standard magnesium counterion does not greatly promote the adsorption of DNA, implying that the effect is specific to RNA and may be useful in boronate-based RNA separations. RNA adsorption isotherms exhibit sharp transitions as functions of temperature, and these transitions occur at different temperatures with Mg2+ and with Ba2+. Adsorption affinity and capacity were found to increase markedly at lower temperatures, suggestive of an enthalpically favored interaction process. The stoichiometric displacement parameter, Z, in Ba2+ buffer is three times the value in Mg2+ buffer, and is close to unity.

NASA Discipline Environmental Health↗

DOE OSTI2025

Development of an ERT‐Based Framework for Bentonite Buffers Monitoring From Laboratory Tests: 1. Characterizing Thermal–Hydrological–Mechanical Processes

Abstract Bentonite clay is widely used in engineered barrier systems for the permanent disposal of high‐level radioactive waste due to its low permeability, high swelling capacity, and thermal stability. However, the complex thermal‐hydrological‐mechanical (THM) processes induced by heating from decaying radioactive waste and hydration from surrounding rock can lead to heterogeneous changes that are difficult to measure and predict. This study develops an Electrical Resistivity Tomography (ERT)‐based framework for monitoring THM processes, progressing from sample‐scale to bench‐scale tests, to inform field‐scale applications. Sample‐scale tests analyzed small bentonite samples under controlled variations in water content, temperature, and porosity to establish fundamental resistivity relationships. Bench‐scale tests involved larger bentonite columns subjected to heating (up to 200°C) and hydration under controlled pressure, simulating repository conditions. ERT measurements, complemented by X‐ray CT imaging, temperature monitoring, and tracing sensors, revealed coupled THM processes, such as hydration‐induced compression, swelling, and thermal gradients, leading to complex resistivity patterns. The results demonstrate the potential of ERT for capturing THM‐induced resistivity changes, though challenges remain in upscaling and quantitative analysis. This study evaluates laboratory test capabilities and proposes future improvements for understanding THM‐induced resistivity responses. A conceptual framework for ERT implementation in field‐scale monitoring is presented, synthesizing findings from both scales and exploring how ERT data can inform long‐term modeling and reduce prediction uncertainties. Overall, this ERT‐based framework offers a robust method for monitoring bentonite buffers, aiding in early issue detection and supporting the safe long‐term disposal of radioactive waste in geological repositories, while highlighting the need for future development. Plain Language Summary Bentonite clay is crucial in engineered barrier systems (EBS) for containing high‐level radioactive waste due to its ability to absorb water, swell, seal and remain stable under high temperatures. When bentonite absorbs water and heats up from radioactive decay, it experiences complex changes in its physical and mechanical properties. Understanding these changes is important for ensuring the long‐term safety and effectiveness of EBS. This study used Electrical Resistivity Tomography (ERT), a non‐invasive method that measures electrical conductivity to monitor these changes during laboratory experiments. The ERT data revealed significant variations in resistivity corresponding to changes in water content, temperature, and density, providing detailed spatial and temporal insights into the behavior of bentonite. These findings enhance our ability to predict the long‐term performance of bentonite barriers, ensuring the safe containment of radioactive waste. By improving our understanding of bentonite's behavior, this research supports the development of more reliable and effective barrier systems for radioactive waste disposal, protecting the environment and public health. Key Points ERT monitoring was employed to capture resistivity changes in bentonite during controlled heating and hydration experiments, providing insights into THM processes ERT data reveal significant resistivity changes correlated with water content, temperature, and mechanical effects, enhancing the understanding of THM dynamics in bentonite This study explores the potential of the framework for application in field‐scale EBS monitoring, emphasizing the need for integrating additional geophysical methods for comprehensive subsurface imaging

Chen, Hang↗

DOE OSTI2022

Low-Oxidized Siloxene Nanosheets with High Capacity, Capacity Retention, and Rate Capability in Lithium-Based Batteries

The mechanical degradation experienced by Si electrodes during Li (de)alloying reactions can potentially be mitigated by using Si-based materials with layered 2D geometries. Such materials are expected to exhibit favorable mechanical properties and be capable of buffering the volume change associated with (de)lithitation. In this work, 2D siloxene nanosheets are synthesized using a facile topotactic reaction followed by ultrasonication as an exfoliation step. Here, detailed structural and chemical characterization via electron microscopy, X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy is conducted, revealing a low-oxidized siloxene nanosheet material with only 15% surface Si-oxide. The obtained siloxene nanosheets are tested as Li-ion negative electrodes in lithium-based electrochemical cells. The cells exhibit high rate capability with a capacity of 935 mAh g –1 at 3200 mA g –1 and ≈99.5% coulombic efficiency. The inclusion of fluoroethylene carbonate (FEC) in the electrolyte improves capacity retention over 200 cycles from 13% to 77% at 1000 mA g –1 . This behavior is attributed to the FEC decomposition forming a solid electrolyte interphase (SEI) with higher ion conductivity and robust LiF/Li x PO y F z content, as characterized via XPS Raman spectroscopy.

25 ENERGY STORAGE↗

NASA NTRS1982

Queueing analysis of synchronous time division multiplexing with individual source buffering

Synchronous time division multiplexing is analyzed. Packets of information arrive at the system as a compound Poisson process, and are transmitted only during individual periodic intervals. Packet arrivals are blocked (lost) if the system has a finite capacity and is congested. Using the theory of semiregenerative processes, the distribution of the number of packets in the system (system size) is found. This nonstationary distribution is used to determine the complete system behavior, including the delay distributions, the blocking probability, and the density of the system size at arrival instants. Numerical examples illustrate applications of the results given.

Clare, L.↗

NASA NTRS1991

Deep FIFO Surge Buffer

First-in/first-out (FIFO) temporarily stores short surges of data generated by data-acquisition system at excessively high rate and releases data at lower rate suitable for processing by computer. Size and complexity reduced while capacity enhanced by use of newly developed, sophisticated integrated circuits and by "byte-folding" scheme doubling effective depth and data rate.

Temple, Gerald↗

DOE OSTI2022

Optimal control to handle variations in moisture content and reactor in-feed rate

The variations in feedstock characteristics, such as moisture and particle size distribution, lead to an inconsistent flow of feedstock from the biomass pre-processing system to the reactor in-feed system. These inconsistencies result in low on-stream times at the reactor in-feed equipment. This research develops an optimal process control method for a biomass pre-processing system comprised of milling and densification operations to provide the consistent flow of feedstock to a reactor's throat. This method uses a mixed-integer optimization model to identify optimal bale sequencing, equipment in-feed rate, and buffer location and size in the biomass pre-processing system. This method, referred to as the hybrid process control (HPC), aims to maximize throughput over time. We compare HPC with a baseline feed forward process control. Our case study based on switchgrass finds that HPC reduces the variation of a reactor's feeding rate by up to 100% without increasing the operating cost of the biomass pre-processing system for biomass with moisture ranging from 10 to 25%. Additionally, HPC reduces the cost of processing biomass by 0.36%–2.22%, and reduces processing time by 0.35%-2.24%. Furthermore, a biorefinery can adapt HPC to achieve its design capacity.

09 BIOMASS FUELS↗

DOE OSTI2022

In-situ synthesis of porous metal fluoride@carbon composite via simultaneous etching/fluorination enabled superior Li storage performance

Transition metal fluorides as Li-free conversion-type cathode materials have high theoretical specific capacities, however, their preparation strategy, sluggish electrochemical kinetic and poor cyclability have impeded their wide adoption in lithium-ion batteries. Herein, a facile in-situ synthesis of porous metal-fluoride-carbon composites is accomplished via simultaneous polytetrafluorethylene-based hard template etching and metal fluorination. This not only facilitates fast electron transfer and lithium-ion diffusion kinetics, but also buffers severe volume fluctuation during lithiation/delithation and enables the formation of a uniform and thin Li 2 CO 3 /LiF-rich cathode-electrolyte interphase. Here, as a proof of concept, the as-prepared porous FeF 3 @C (p-FeF 3 @C) indeed exhibits a high specific capacity of 230 mAh g -1 at 0.1 C together with an excellent capacity retention of 92.5% at 1 C for 200-cycles. Moreover, the practicality of the strategy is demonstrated by the superb electrochemical performance of the full-cells coupled with pre-lithiated graphite anodes. Therefore, the proposed novel synthetic strategy will enlighten the future design of high-performance metal-fluoride-carbon composites with porous structure for energy storage applications.

25 ENERGY STORAGE↗

DOE OSTI2022

High‐Energy‐Density Chelated Chromium Flow Battery Electrolyte at Neutral pH

Abstract High‐concentration operation of redox flow batteries (RFBs) is essential for increasing their energy‐storage capacity, but non‐acidic electrolytes struggle to achieve the high concentrations of metal ions dissolved in acid, limiting the development of energy‐dense neutral pH electrolytes. We report neutral pH RFB operation of chromium 1,3‐propylenediaminetetraacetate (CrPDTA) at concentrations of 1.2 M at room temperature and 1.6 M at 40 °C, demonstrating 60% higher negolyte capacity, up to 42.9 Ah L −1 , than previously reported for non‐additive‐utilizing solutions of this promising material. With extended full cell cycling, we demonstrate the importance of buffer selection and pH when using the Fumasep E‐620(K) membrane. Finally, we expand the pH operation range of CrPDTA to pH 7, which when cycled at 100 mA cm −2 against a ferrocyanide posolyte demonstrated excellent coulombic efficiencies >99.7% and energy efficiencies >87%, while operating at almost 700 mV more negative than the thermodynamic hydrogen evolution window.

Chemistry↗

NASA NTRS1991

A RAM architecture for concurrent access and on-chip testing

A novel RAM architecture supporting concurrent memory access and on-chip testing (CMAT) is proposed. A large-capacity memory chip is decomposed into test neighborhoods (TNDs), each of which is tested independently. When there are data stored in a TND, the data are saved into a buffer before testing the TND, and the TND's contents are restored using buffered data after testing the TND. If an external request is not made to the TND, the request can be directed to the addressed memory cells. Otherwise, the buffered data can be loaded back into the TND, or the request is detoured to a corresponding buffer. By deriving an analytical model, the performance penalty and hardware overhead of the CMAT architecture are shown to be very small.

Liu, Jyh-Charn↗

NASA NTRS1992

Proposal for massively parallel data storage system

An architecture for integrating large numbers of data storage units (drives) to form a distributed mass storage system is proposed. The network of interconnected units consists of nodes and links. At each node there resides a controller board, a data storage unit and, possibly, a local/remote user-terminal. The links (twisted-pair wires, coax cables, or fiber-optic channels) provide the communications backbone of the network. There is no central controller for the system as a whole; all decisions regarding allocation of resources, routing of messages and data-blocks, creation and distribution of redundant data-blocks throughout the system (for protection against possible failures), frequency of backup operations, etc., are made locally at individual nodes. The system can handle as many user-terminals as there are nodes in the network. Various users compete for resources by sending their requests to the local controller-board and receiving allocations of time and storage space. In principle, each user can have access to the entire system, and all drives can be running in parallel to service the requests for one or more users. The system is expandable up to a maximum number of nodes, determined by the number of routing-buffers built into the controller boards. Additional drives, controller-boards, user-terminals, and links can be simply plugged into an existing system in order to expand its capacity.

Mansuripur, M.↗