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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 397 records · Page 22
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Surface and Bulk Stabilization of Silicon Anodes with Mixed-Multivalent Additives: Ca(TFSI) 2 and Mg(TFSI) 2

Here, silicon is drawing attention as the upcoming anode material for the next generation of lithium-ion batteries due to its higher capacity compared to commercial graphite. However, silicon anions formed during lithiation are highly reactive with binder and electrolyte components creating an unstable SEI layer and limiting the calendar life of silicon anodes. The reactivity of lithium silicide and the formation of an unstable SEI layer is mitigated by utilizing the use of a mixture of Ca and Mg multivalent cations as an electrolyte additive for Si anodes to improve their calendar life. The effect of mixed salts on the bulk and surface of silicon anodes was studied by multiple structural characterization techniques. Ca and Mg ions in the electrolyte formed relatively thermodynamically stable quaternary Li-Ca-Mg-Si Zintl phases in an in-situ fashion and more stable and denser SEI layer on the Si particles. These in turn protect silicon particles against side reactions with electrolytes in a coin cell. The full cell with the mixed cation electrolyte demonstrates enhanced calendar life performance with lower measured current and current leakage than that of the baseline electrolyte due to reduced side reactions. Electron Microscopy, HRXRD, and solid-state NMR results showed that electrodes with mixed cations tended to have less cracking on the electrode surface compared to Si electrodes with Gen2 + FEC and the presence of mixed cations enhances cation migration and formation of quaternary Zintl phases stabilizing bulk and forming a more stable SEI.

25 ENERGY STORAGE↗
NASA NTRS2017

Silicon-Based Lithium-Ion Capacitor for High Energy and High Power Application

Si-based Li-ion capacitor has been developed and demonstrated. The results show it is feasible to improve both power density and energy density in this configuration. The applied current density impacts the power and energy density: low current favors energy density while high current favors power density. Active carbon has a better rate capability than Si. Next StepsFuture Directions. Si electrode needs to be further studied and improved. Further optimization of SiAC ratio and evaluation of its impact on energy density and power density.

Wu, James J.↗
NASA NTRS1980

DOE/JPL advanced thermionic technology program

Accomplishments in the DOE program include: continuing stable output from the combustion life test of the one-inch diameter hemispherical silicon carbine diode (Converter No. 239) at an emitter temperature of 1730 K for a period of over 4200 hours; construction of four diode module completed; favorable results obtained from TAM combustor-gas turbine system analyses; and obtained a FERP work function of 2.3 eV with the W(100)-O-Zr-C electrode. JPL program accomplishments include: the average minimum barrier index of the last six research diodes built with sublimed molybdenum oxide collectors was 20 eV (WHK).

Source record↗
DOE OSTI2020

Effect of Water Concentration in LiPF 6 -Based Electrolytes on the Formation, Evolution, and Properties of the Solid Electrolyte Interphase on Si Anodes

A trace amount of water in an electrolyte is one of the factors detrimental to the electrochemical performance of silicon (Si)-based lithium-ion batteries that adversely affect the formation and evolution of the solid electrolyte interphase (SEI) on Si-based anodes and change its properties. Thus far, a lack of fundamental and mechanistic understanding of SEI formation, evolution, and properties in the presence of water has inhibited efforts to stabilize the SEI for improved electrochemical performance. As such, we investigated the SEI formed in a Gen2 electrolyte (1.2 M LiPF6 in ethylene carbonate/ethyl methyl carbonate, 3:7 wt %, water content: <10 ppm) with and without additional water (50 ppm) at varying potentials (1.0, 0.5, 0.2, and 0.01 V vs Li/Li + ). The impact of additional water on the morphological, (electro)chemical, and structural properties of SEI was studied using microscopic (atomic force microscopy and scanning spreading resistance microscopy) and spectroscopic (X-ray photoelectron spectroscopy, attenuated total reflection Fourier-transform infrared spectroscopy, and time-of-flight secondary ion mass spectrometry) techniques. The SEI exhibits both potential- and water concentration-dependent trends in its morphology and chemical composition. The presence of additional water in the electrolyte causes parasitic reactions, which onset at ~1.0 V, resulting in a reduction of electrolyte components and result in the formation of an insulating, fluorophosphate-rich SEI. In addition, hydrolysis of LiPF 6 creates hydrofluoric acid, which reacts with the surface oxide layer on the Si electrode, leading to a pitted and inhomogeneous SEI structure.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Enhanced performance of Bi 2 S 3 /TiO 2 heterostructure composite films for solar cell applications

Day to day energy production is shifting towards renewable energy sources as these sources become more economically viable while being less polluting to operate; solar energy has become one of the major sources of renewable energy. However, it currently relies on ultra-pure silicon ingots to produce commercial silicon photovoltaics, which prevents the cost of electricity being produced to compete with non-renewable energy production. A viable low-cost alternative for silicon based cells would be dye-sensitized solar cells (DSSCs), which are easier and cheaper to manufacture as they do not require expensive and delicate raw materials to make. Moreover, they could be made semi-flexible which allows for a greater variety of applications. A DSSC consists of three components, a photo-electrode, an electrolyte and a counter-electrode. When exposed to incident light, the complex photosensitizers in the photoelectrode release electrons which are transported to the external load, leaving the photoelectrode in an oxidized state. The electrons are collected by the counter electrode and used to reduce the electrolyte. This charged electrolyte then reduces the positively charged photoelectrode, allowing the process to begin again. To improve the efficiency of this process, we explore the use of bismuth sulfide (Bi 2 S 3 ) and titanium oxide (TiO 2 ) composite as photoelectrode material and investigate their impact on the efficiency of DSSC.

14 SOLAR ENERGY↗
NASA NTRS1978

Advanced solid electrolyte cell for CO2 and H2O electrolysis

A solid electrolyte cell with improved sealing characteristics was examined. A tube cell was designed, developed, fabricated, and tested. Design concepts incorporated in the tube cell to improve its sealing capability included minimizing the number of seals per cell and moving seals to lower temperature regions. The advanced tube cell design consists of one high temperature ceramic cement seal, one high temperature gasket seal, and three low temperature silicone elastomer seals. The two high temperature seals in the tube cell design represent a significant improvement over the ten high temperature precious metal seals required by the electrolyzer drum design. For the tube cell design the solid electrolyte was 8 mole percent yttria stabilized zirconium oxide slip cast into the shape of a tube with electrodes applied on the inside and outside surfaces.

Shumar, J. W.↗
DOE OSTI2021

In Situ Synthesis of Graphene-Coated Silicon Monoxide Anodes from Coa-Derived Humic Acid for High-Performance Lithium-Ion Batteries

Silicon monoxide (SiO) is attaining extensive interest amongst silicon-based materials due to its high capacity and long cycle life; however, its low intrinsic electrical conductivity and poor coulombic efficiency strictly limit its commercial applications. Here low-cost coal-derived humic acid (HA) is used as a feedstock to synthesize in-situ graphene-coated disproportionated SiO (D-SiO@G) anode with a facile method. HRTEM and XRD confirm the well-coated graphene layers on an SiO surface. Scanning Transmission X-ray Microscopy (STXM) and X-ray Absorption Near-Edge Structure (XANES) spectra analysis indicate that the graphene coating effectively hinders the side-reactions between the electrolyte and SiO particles . As a result, the D-SiO@G anode presents an initial discharge capacity of 1937.6 mAh g -1 at 0.1 A g -1 and an initial coulombic efficiency (ICE) of 78.2%. High reversible capacity (1023 mAh g -1 at 2.0 A g -1 ), excellent cycling performance ( 72.4% capacity retention after 500 cycles at 2.0 A g -1 ), and rate capability (774 mAh g -1 at 5 A g -1 ) results are substantial. Full coin cells assembled with LiFePO 4 electrodes and D-SiO@G electrodes display impressive rate performance. These results indicate a promising potential for practical use in high-performance lithium-ion batteries.

25 ENERGY STORAGE↗
NASA NTRS1990

Memory switches based on metal oxide thin films

MnO.sub.2-x thin films (12) exhibit irreversible memory switching (28) with an OFF/ON resistance ratio of at least about 10.sup.3 and the tailorability of ON state (20) resistance. Such films are potentially extremely useful as a connection element in a variety of microelectronic circuits and arrays (24). Such films provide a pre-tailored, finite, non-volatile resistive element at a desired place in an electric circuit, which can be electrically turned OFF (22) or disconnected as desired, by application of an electrical pulse. Microswitch structures (10) constitute the thin film element, contacted by a pair of separate electrodes (16a, 16b) and have a finite, pre-selected ON resistance which is ideally suited, for example, as a programmable binary synaptic connection for electronic implementation of neural network architectures. The MnO.sub.2-x microswitch is non-volatile, patternable, insensitive to ultraviolet light, and adherent to a variety of insulating substrates (14), such as glass and silicon dioxide-coated silicon substrates.

Ramesham, Rajeshuni↗
DOE OSTI2022

High-Density, Actively Multiplexed µECoG Array on Reinforced Silicone Substrate

Simultaneous interrogation of electrical signals from wide areas of the brain is vital for neuroscience research and can aid in understanding the mechanisms of brain function and treatments for neurological disorders. There emerges a demand for development of devices with highly conformal interfaces that can span large cortical regions, have sufficient spatial resolution, and chronic recording capability while keeping a small implantation footprint. In this work, we have designed 61 channel and 48 channel high-density, cortical, micro-electrocorticographic electrode arrays with 400 µm pitch on an ultra-soft but durable substrate. We have also developed a custom multiplexing integrated circuit (IC), methods for packaging the IC in a water-tight liquid crystal polymer casing, and a micro-bonding method for attaching the electronics package to the electrode array. With the integrated multiplexer, the number of external wire connections can be reduced to 16 wires, thereby diminishing the invasive footprint of the device. Both the electrode array and IC were tested in vivo in a rat model to demonstrate the ability to sense finely-localized electrophysiological signals.

Rachinskiy, Iakov↗
NASA NTRS1985

Enhanced adhesion of films to semiconductors or metals by high energy bombardment

Films (12) of a metal such as gold or other non-insulator materials are firmly bonded to other non-insulators such as semiconductor substrates (10), suitably silicon or gallium arsenide by irradiating the interface with high energy ions. The process results in improved adhesion without excessive doping and provides a low resistance contact to the semiconductor. Thick layers can be bonded by depositing or doping the interfacial surfaces with fissionable elements or alpha emitters. The process can be utilized to apply very small, low resistance electrodes (78) to light-emitting solid state laser diodes (60) to form a laser device 70.

Tombrello, Thomas A.↗
DOE OSTI2023

Platinum group metal-free (PGM-free) integrated tandem junction photoelectrochemical (PEC) water splitting devices (Final Technical Report)

This project involves using solar light, a photoabsorber, and a catalyst to split water and produce hydrogen. The Department of Energy (DOE) targets for integrated photoelectrochemical (PEC) cells emphasize cost (electrode cost < $200/m 2 ), performance (> 15% solar to hydrogen (STH) efficiency), and stability (> 6 months electrode lifetime), but most approaches skew toward one specific metric. This project exploited interfacial integration of platinum group metal-free (PGM-free) catalysts on the high performance and high value tandem solar cells to attain or exceed the DOE benchmark STH energy conversion efficiency and durability. This was investigated in two thrusts by developing two PEC devices for direct comparison: the first is a high-performance monolithic device based on state-of-the-art GaInP 2 /GaAs tandem solar cells developed at National Renewable Energy Laboratory (NREL), and the second is a high-value device based on earth-abundant wide band gap photoabsorber materials including oxynitride and hybrid organic-inorganic perovskite (HOIP) coupled with commercial narrow band gap silicon (Si). Both these devices were paired with electrocatalysts developed for this purpose at Rutgers University by adapting them to thin films on the photoabsorbers. These catalysts are based on the hydrogen evolution reaction (HER) catalysts (Ni 5 P 4 ), oxygen evolution reaction (OER) catalysts (LiCo 2 O 4 ) previously developed at Rutgers for high-efficiency electrolyzers. For using the high-performance tandem solar cell and Ni 5 P 4 catalysts, we achieved a durability of > 200 h at a STH efficiency of > 10%. For using the high-value wide band gap single junction solar cells on n + Si, we achieved 0.73 mA/cm 2 at 1.23V vs reversible hydrogen electrode (RHE) and -15.9 mA/cm 2 at 0V vs RHE using the oxynitride- and HOIP-based photoelectrodes, respectively. After comparing their photocurrent densities, we down selected the HOIP photoabsorber to couple Si for fabrication of a tandem photocathode. However, due to the COVID-19 pandemic, both the laboratories at Rutgers and NREL were locked down for three months and reopened only partially in 2020. The HOIP/Si tandem photocathode using robust nickel phosphide thin film catalysts cannot be developed within the project period, which is expected to achieve a STH efficiency of > 20%. Also, the low-cost LiCo 2 O 4 OER catalysts need to replace the benchmark IrO 2 for evaluation. Finally, techonomic analysis of full high-performance and high-value integrated PEC devices needs to be carried out for comparison in terms of cost.

08 HYDROGEN↗
DOE OSTI2021

Mechanical studies of the solid electrolyte interphase on anodes in lithium and lithium ion batteries

A stable solid electrolyte interphase (SEI) layer is key to high performing lithium ion batteries for metrics such as calendar and cycle life. The SEI must be mechanically robust to withstand large volumetric changes in anode materials such as lithium and silicon, so understanding the mechanical properties and behavior of the SEI is essential for the rational design of artificial SEI and anode form factors. The mechanical properties and mechanical failure of the SEI are challenging to study, because the SEI is thin at only ~ 10 – 200 nm thick and is air sensitive. Furthermore, the SEI changes as a function of electrode material, electrolyte and additives, temperature, potential, and formation protocols. A variety of in situ and ex situ techniques have been used to study the mechanics of the SEI on a variety of lithium ion battery anode candidates; however, there hasn't been a succinct review of the findings thus far. Because of the difficultly of isolating the true SEI and its mechanical properties, there have been a limited number of studies that can fully de-convolute the SEI from the anode it forms on. A review of past research will be helpful for culminating current knowledge and helping to inspire new innovations to better quantify and understand the mechanical behavior of the SEI. This review will summarize the different experimental and theoretical techniques used to study the mechanics of SEI on common lithium ion battery anodes and their strengths and weaknesses.

25 ENERGY STORAGE↗
DOE OSTI2021

1000 Wh L−1 lithium-ion batteries enabled by crosslink-shrunk tough carbon encapsulated silicon microparticle anodes

Abstract Microparticulate silicon (Si), normally shelled with carbons, features higher tap density and less interfacial side reactions compared to its nanosized counterpart, showing great potential to be applied as high-energy lithium-ion battery anodes. However, localized high stress generated during fabrication and particularly, under operating, could induce cracking of carbon shells and release pulverized nanoparticles, significantly deteriorating its electrochemical performance. Here we design a strong yet ductile carbon cage from an easily processing capillary shrinkage of graphene hydrogel followed by precise tailoring of inner voids. Such a structure, analog to the stable structure of plant cells, presents ‘imperfection-tolerance’ to volume variation of irregular Si microparticles, maintaining the electrode integrity over 1000 cycles with Coulombic efficiency over 99.5%. This design enables the use of a dense and thick (3 mAh cm–2) microparticulate Si anode with an ultra-high volumetric energy density of 1048 Wh L–1 achieved at pouch full-cell level coupled with a LiNi0.8Co0.1Mn0.1O2 cathode.

25 ENERGY STORAGE↗
NASA NTRS1990

Lunar oxygen and metal for use in near-Earth space: Magma electrolysis

Because it is energetically easier to get material from the Moon to Earth orbit than from the Earth itself, the Moon is a potentially valuable source of materials for use in space. The unique conditions on the Moon, such as vacuum, absence of many reagents common on the Earth, and the presence of very nontraditional ores suggest that a unique and nontraditional process for extracting materials from the ores may prove the most practical. With this in mind, an investigation of unfluxed silicate electrolysis as a method for extracting oxygen, iron, and silicon from lunar regolith was initiated and is discussed. The advantages of the process include simplicity of concept, absence of need to supply reagents from Earth, and low power and mass requirements for the processing plant. Disadvantages include the need for uninterrupted high temperature and the highly corrosive nature of the high-temperature silicate melts which has made identifying suitable electrode and container materials difficult.

Colson, Russell O.↗
DOE OSTI2021

A Micrometer‐Sized Silicon/Carbon Composite Anode Synthesized by Impregnation of Petroleum Pitch in Nanoporous Silicon

Porous silicon (Si)/carbon nanocomposites have been extensively explored as a promising anode material for high-energy lithium (Li)-ion batteries (LIBs). However, shrinking of the pores and sintering of Si in the nanoporous structure during fabrication often diminishes the full benefits of nanoporous Si. Herein, a scalable method is reported to preserve the porous Si nanostructure by impregnating petroleum pitch inside of porous Si before high-temperature treatment. The resulting micrometer-sized Si/C composite maintains a desired porosity to accommodate large volume change and high conductivity to facilitate charge transfer. It also forms a stable surface coating that limits the penetration of electrolyte into nanoporous Si and minimizes the side reaction between electrolyte and Si during cycling and storage. A Si-based anode with 80% of pitch-derived carbon/nanoporous Si enables very stable cycling of a Si||Li(Ni0.5Co0.2Mn0.3)O 2 (NMC532) battery (80% capacity retention after 450 cycles). It also leads to low swelling in both particle and electrode levels required for the next generation of high-energy LIBs. In conclusion, the process also can be used to preserve the porous structure of other nanoporous materials that need to be treated at high temperatures.

anode materials↗
DOE OSTI2023

Consequences of utilizing a redox-active polymeric binder in Li-ion batteries

Development of new polymeric binders can help enable the use of silicon-rich anodes in Li-ion batteries, by providing stronger adhesion to the active material particles. The compositional features that improve interfacial interactions and mechanical properties can often impart electronic conductivity and redox activity to these polymers, which are generally seen as beneficial to cell performance. Alternatively, it is also possible that the addition of charge-transferring centers to the electrode can accelerate cell degradation. Here, we use an aromatic polyimide (∼320 mA h/g of reversible capacity) to explore how a redox-active conductive polymer can affect cell performance. We demonstrate that the lithiated polymer is less stable than the traditional binders upon storage, leading to increased rates of calendar aging. Furthermore, we determine that the adhesion properties of the polymer deteriorate upon repeated cycling, to an extent that is proportional to the degree of delithiation of the binder. More critically, we establish that progressive degradation of the redox behavior of the polymer leads to the release of “extra” Li + into the cell, which can give the false perception of good performance even under conditions of poor stability. In conclusion, our work suggests that redox-active conductive binders can sometimes be detrimental to cell performance, and that works evaluating new polymers must include careful experimental validation under realistic conditions.

25 ENERGY STORAGE↗
DOE OSTI2021

Fabrication of Silicon Sensors Based on Low-Gain Avalanche Diodes

Low-Gain Avalanche Diodes are a recently-developed class of silicon sensors. Characterized by an internal moderate gain that enhances the signal amplitude and if built on thin silicon substrates of a few tens of microns, they feature fast signals and exhibit excellent timing performance. Thanks to their fast timing they are planned to be exploited in timing detectors in High-Energy Physics experiments, for example for the upgrades of the ATLAS and CMS detectors at the High Luminosity Large Hadron Collider (HL-LHC) at CERN. However, to achieve a spatially uniform multiplication a large pixel pitch is needed, preventing a fine spatial resolution. To overcome this limitation, the AC-coupled LGAD approach was introduced. In this type of device, metal electrodes are placed over an insulator at a fine pitch, and signals are capacitively induced on these electrodes. The fabrication technology is similar for the two LGAD families, although a fine tuning of a few process parameters needs to be carefully studied. Other R&D efforts towards detectors that can simultaneously provide good time and spatial resolution, based on the LGAD concept, are under way. These efforts aim also to mitigate the loss of performance at high irradiation fluences due to the acceptor removal within the gain layer. In this paper we describe the main points in the fabrication of LGADs and AC-LGADs in a clean-room. We also discuss novel efforts carried on related topics.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2020

Laser writing of nitrogen-doped silicon carbide for biological modulation

Conducting or semiconducting materials embedded in insulating polymeric substrates can be useful in biointerface applications; however, attainment of this composite configuration by direct chemical processes is challenging. Laser-assisted synthesis has evolved as a fast and inexpensive technique to prepare various materials, but its utility in the construction of biophysical tools or biomedical devices is less explored. Here, we use laser writing to convert portions of polydimethylsiloxane (PDMS) into nitrogen-doped cubic silicon carbide (3C-SiC). The dense 3C-SiC surface layer is connected to the PDMS matrix via a spongy graphite layer, facilitating electrochemical and photoelectrochemical activity. We demonstrate the fabrication of arbitrary two-dimensional (2D) SiC-based patterns in PDMS and freestanding 3D constructs. To establish the functionality of the laser-produced composite, we apply it as flexible electrodes for pacing isolated hearts and as photoelectrodes for local peroxide delivery to smooth muscle sheets.

59 BASIC BIOLOGICAL SCIENCES↗