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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 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Spatial quantification of dynamic inter and intra particle crystallographic heterogeneities within lithium ion electrodes

The performance of lithium ion electrodes is hindered by unfavorable chemical heterogeneities that pre-exist or develop during operation. Time-resolved spatial descriptions are needed to understand the link between such heterogeneities and a cell's performance. Here, operando high-resolution X-ray diffraction-computed tomography is used to spatially and temporally quantify crystallographic heterogeneities within and between particles throughout both fresh and degraded Li x Mn 2 O 4 electrodes. This imaging technique facilitates identification of stoichiometric differences between particles and stoichiometric gradients and phase heterogeneities within particles. Through radial quantification of phase fractions, the response of distinct particles to lithiation is found to vary; most particles contain localized regions that transition to rock salt LiMnO 2 within the first cycle. Other particles contain monoclinic Li 2 MnO 3 near the surface and almost pure spinel LixMn2O4 near the core. Following 150 cycles, concentrations of LiMnO 2 and Li 2 MnO 3 significantly increase and widely vary between particles.

25 ENERGY STORAGE↗
DOE OSTI2020

Spatial dynamics of lithiation and lithium plating during high-rate operation of graphite electrodes

The principal inhibitor of fast charging lithium ion cells is the graphite negative electrode, where favorable conditions for lithium plating occur at high charge rates, causing accelerated degradation and safety concerns. The local response of graphite, both at the electrode and particle level, when exposed to fast charging conditions of around 6C is not well understood. Consequently, the conditions that lead to the onset of lithium plating, as well as the local dynamics of lithium plating and stripping, have also remained elusive. Here, we use high-speed (100 Hz) pencil-beam X-ray diffraction to repeatedly raster along the depth of a 101 μm thick graphite electrode in 3 μm steps during fast (up to 6C) charge and discharge conditions. Consecutive depth profiles from separator to current collector were each captured in 0.5 seconds, giving an unprecedented spatial and temporal description of the state of the electrode and graphite's staging dynamics during high rate conditions. The electrode is preferentially activated near the separator, and the non-uniformity increases with rate and is influenced by free-energy barriers between graphite's lithiation stages. The onset of lithium plating and stripping was quantified, occurring only within the first 15 μm from the separator. The presence of lithium plating changed the behavior of the underlying graphite, such as causing co-existence of LiC 6 and graphite in the fully discharged state. Finally, the staging behavior of graphite at different rates was quantified, revealing a high dependency on rate and drastic hysteresis between lithiation and delithiation.

25 ENERGY STORAGE↗
DOE OSTI2022

Irradiation-induced Degradation of Surface Acoustic Wave Devices Fabricated on Bulk AlN

Here, recent work to evaluate the prospects for surface acoustic wave (SAW) devices fabricated on bulk aluminum nitride (AlN) for elevated temperature and radiation environments is reported and discussed. The design and fabrication of an array of SAW devices using commercial wafers is described, including the non-standard fabrication approach taken to overcome the stress-induced warpage of the 50 mm diameter AlN substrates. Radio frequency performance characterization of the SAW devices, with resonance frequencies ranging from 0.5 GHz to 1.5 GHz, is described. The linear temperature coefficient of frequency (TCF) near room temperature was measured and is compared to theoretical results from other investigators. Further, the effects of 8 MeV Al ion irradiation at 300°C and 500°C to damage levels of 0.01, 0.1 and 1 displacements per atom (dpa), as a proxy for neutron irradiation, was investigated. The ion irradiation damage was observed to decrease the SAW resonant frequency, and this effect is characterized and discussed. Significant degradation in the conductivity of the Ti/Al electrodes of the SAW devices was also observed and characterized. These experimental results provide a basis for further investigation of the prospects for development of SAW sensor devices in bulk AlN material for application in elevated temperature and radiation environments.

36 MATERIALS SCIENCE↗
NASA NTRS1982

Effects of the mode of storage on the capacity fading of the sintered nickel electrodes

A systematic investigation of the effect of temperature and two conditions of storage, shortened and open circuit, on the capacity fading of sintered nickel electrodes in NiCd batteries was conducted. All testing was done on sintered electrodes in flooded cells. Cycling tests to measure the capacity were performed at room temperature. The capacity out to one volt, a capacity useful for satellite applications. Test results indicated that: the shortened electrode showed a higher rate of loss than the open circuit electrodes; there was an increase in both modes with an increase in temperature; there was a loss of capacity with time of storage; a general degradation was observed as a function of time; shortened electrodes showed a higher end of charge than the open circuit ones; and at room temperature there was a lower loss in the open circuit electrode than in the shortened one.

Vyes, B.↗
NASA NTRS2014

2014 NEPP Tasks Update for Ceramic and Tantalum Capacitors

Presentation describes recent development in research on MnO2, wet, and polymer tantalum capacitors. Low-voltage failures in multilayer ceramic capacitors and techniques to reveal precious metal electrode (PME) and base metal electrode (BME) capacitors with cracks are discussed. A voltage breakdown technique is suggested to select high quality low-voltage BME ceramic capacitors.

ceramic capacitors↗
NASA NTRS1982

Impact of uniform electrode current distribution on ETF

A basic reason for the complexity and sheer volume of electrode consolidation hardware in the MHD ETF Powertrain system is the channel electrode current distribution, which is non-uniform. If the channel design is altered to provide uniform electrode current distribution, the amount of hardware required decreases considerably, but at the possible expense of degraded channel performance. This paper explains the design impacts on the ETF electrode consolidation network associated with uniform channel electrode current distribution, and presents the alternate consolidation designs which occur. They are compared to the baseline (non-uniform current) design with respect to performance, and hardware requirements. A rational basis is presented for comparing the requirements for the different designs and the savings that result from uniform current distribution. Performance and cost impacts upon the combined cycle plant are discussed.

Bents, D. J.↗
DOE OSTI2021

The Impact of Different Substituents in Fluorinated Cyclic Carbonates in the Performance of High Voltage Lithium-Ion Battery Electrolyte

Ethylene carbonate (EC) has been used as the Solid-Electrolyte Interphase (SEI) former in the conventional electrolyte for decades. However, its low anodic stability leads to severe capacity decay during cycling under high voltage operation. Therefore, finding a viable electrolyte with high anodic stability and the ability to form robust SEI for high voltage lithium-ion batteries is of primary importance. In this study, a series of electrolytes containing various fluorinated cyclic carbonates as the SEI former have been designed, synthesized and evaluated. Linear sweep voltammetry study suggested that fluorinated cyclic carbonates generally possess higher anodic stability than EC. Based on the cycling performance of LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NMC532)/ graphite full cells, the electrolyte with DFEC/FEMC (1.0 M LiPF 6 ) inhibited the oxidation side reaction on the cathode and forms a vigorous SEI on the anode. The high voltage NMC532/Graphite cell utilizing the novel electrolyte exhibits excellent cycling durability under both room and elevated temperature. The superior performance of the DFEC based electrolyte was further unveiled by SEM, EDAX and XRD. Both the anode and cathode of the full cell employing DFEC based electrolyte retained their intrinsic structures after cycling while the electrodes cycled in conventional electrolyte showed severe degradation.

25 ENERGY STORAGE↗
NASA NTRS1987

Traveling-wave-tube efficiency improvement by a low-cost technique for deposition of carbon on multistage depressed collector

A simple method of improving the traveling-wave-tube (TWT) and multistage depressed collector (MDC) efficiency has been demonstrated. The efficiency improvement was produced by the application of a thin layer of carbon to the copper electrodes of the MDC by means of a rapid, low-cost technique involving the pyrolysis of hydrocarbon oil in electric arc discharges. Experimental results with a representative TWT and MDC showed an 11 percent improvement in both the TWT and MDC efficiencies as compared to those of the same TWT and MDC efficiencies with bare copper electrode surfaces. An extended test with a 500-W, continuous wave (CW) TWT and small-sized MDC indicated good stability of the carbon coated electrode surfaces after a relatively small initial degradation in TWT overall and apparent MDC efficiencies.

Ebihara, Ben T.↗
NASA NTRS1998

Lifetime Modeling of Tin Electrodes for AMTEC Cells

In order to model the lifetime of the electrochemical cell in an Alkali Metal Thermal to Electric Converter (AMTEC), studies of TiN Electrodes on Beta-alumina solid electrolytes (BASE) have been made to determine the performace parameters over time. The first of a series of experiments in which TiN electrodes are studied in a Vapor Exposure Test Cell is described here, with preliminary results from electrochemical measurements made on the cell. The TiN electrodes tested here perform well, with minimal degradation over 1000 hours of operation at 850 degree C.

Electrochemical↗
DOE OSTI2024

Modeling Ni Coarsening under Humid Atmosphere in the Electrode of Solid Oxide Cells

Ni coarsening is an important degradation mechanism in solid oxide cells. It is reported that Ni coarsening is faster under a humid atmosphere experimentally, but the underline mechanism is not well understood. In this work, Ni coarsening through Ni(OH)x surface diffusion was investigated by a combination of density-functional theory (DFT) and phase-field modeling (PFM). DFT is used to evaluate the surface coverage and diffusivity of Ni(OH)x on Ni (111) surface and the results are used as an input to the PFM to simulate Ni coarsening under humid atmospheres on both reconstructed and synthetic microstructures. It is found that steam partial pressure and microstructure effect alone cannot explain the faster Ni coarsening under a humid atmosphere observed experimentally. Large local overpotential in fuel cell mode is needed to explain the fast Ni coarsening.

Lei, Yinkai↗
NASA NTRS1984

Positive Electrode Fabrication for Bi-polar Ni-h2 Cells

Bi-Polar nickel hydrogen design studies indicated a potential improvement in energy density and specific energy if positive electrodes could be manufactured in configurations of twice or more of the present normal thickness. Such electrodes would have to achieve similar active material loading, utilization, and cycle life to conventional 0.8mm I.P.U. nickel hydrogen electrodes. A capability for producing 1.0mm dry sinter and 1.5mm slurry sinter structures on production processes and equipment was demonstrated. The EPI/USAF electrochemical impregnation process proved capable of loading thick electrodes to 1.60 g/cubic centimeters void or higher. Sample electrodes incurred 2000 high rate stress cycles without significant structural or performance degradation. Formation regimes developed for thin plaque are not optimal for thick plaque and further investigation into electrode capacity build-up would seem warranted. Thick electrode technology development is continuing under other programs and shows promise of fulfilling the projected energy density and specific energy improvements.

Edgar, T. A.↗
DOE OSTI2022

Modeling Ni redistribution in the hydrogen electrode of solid oxide cells through Ni(OH) 2 diffusion and Ni-YSZ wettability change

Ni redistribution in the hydrogen electrodes of solid oxide cells is an important degradation mechanism. Its driving force is still under debate. This work focuses on the interplay between Ni(OH) 2 diffusion and Ni-YSZ wettability change. With a Ni(OH) 2 diffusion model developed in our previous work, we further employ three models for the Ni-YSZ contact angle to quantify the Ni-YSZ wettability change. The microstructure evolutions in a reconstructed Ni-YSZ electrode are simulated under selected experimental operating conditions. It is shown that the phenomenological model can capture the driving force of Ni spreading/detachment on YSZ surface and the Ni migration reported in experiments can be qualitatively reproduced through the competition between Ni(OH) 2 diffusion and Ni-YSZ wettability change. It is also found that the initial microstructure of the active layer and the microstructure characteristics in the support layer can strongly affect the distribution of steam partial pressure and overpotential, hence the Ni redistribution, in the active layer, which may explain the inconsistencies in experiments. Further, our results show that there are two missing pieces in current theory of Ni redistribution: a mechanism of fast Ni diffusion under humid atmosphere and the physical reason behind the Ni spreading/detachment.

25 ENERGY STORAGE↗
DOE OSTI2025

Structural Transformation and Degradation of Cu Oxide Nanocatalysts during Electrochemical CO 2 Reduction

The electrochemical CO 2 reduction reaction (CO 2 RR) holds enormous potential as a carbon-neutral route to the sustainable production of fuels and platform chemicals. The durability for long-term operation is currently inadequate for commercialization, however, and the underlying deactivation process remains elusive. A fundamental understanding of the degradation mechanism of electrocatalysts, which can dictate the overall device performance, is needed. In this work, we report the structural dynamics and degradation pathway of Cu oxide nanoparticles (CuO x NPs) during the CO 2 RR by using in situ small-angle X-ray scattering (SAXS) and X-ray absorption spectroscopy (XAS). The in situ SAXS reveals a reduction in the size of NPs when subjected to a potential at which no reaction products are detected. At potentials where the CO 2 RR starts to occur, CuO x NPs are agglomerated through a particle migration and coalescence process in the early stage of the reaction, followed by Ostwald ripening (OR) as the dominant degradation mechanism for the remainder of the reaction. As the applied potential becomes more negative, the OR process becomes more dominant, and for the most negative applied potential, OR dominates for the entire reaction time. The morphological changes are linked to a gradual decrease in the formation rate for multicarbon products (C 2 H 4 and ethanol). Other reaction parameters, including reaction intermediates and local high pH, induce changes in the agglomeration process and final morphology of the CuO x NPs electrode, supported by post-mortem ex situ microscopic analysis. The in situ XAS analysis suggests that the CuO x NPs reduced into the metallic state before the structural transformation was observed. The introduction of high surface area carbon supports with ionomer coating mitigates the degree of structural transformation and detachment of the CuO x NPs electrode. These findings show the dynamic nature of Cu nanocatalysts during the CO 2 RR and can serve as a rational guideline toward a stable catalyst system under electrochemical conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Editors’ Choice—Necessity to Avoid Titanium Oxide as Electrocatalyst Support in PEM Fuel Cells: A Membrane Durability Study

Pt/TiO 2 as electrocatalyst was found to significantly increase the rate of the membrane chemical degradation in a polymer electrolyte membrane (PEM) fuel cell. The increased degradation was proved to be due to TiO x (TiO 2 or Ti 4 O 7 ), which is widely recognized as a promising corrosion-resistant electrocatalyst support. The membrane degradation (thinning) appears to be preferentially in the side facing anode electrode. Migrated Ti species as a result of TiO x dissolution during fuel cell operation in an acidic environment was quantified by electron probe microanalysis (EPMA). Total fluorine inventory loss of the membrane strongly depends on the quantity of migrated Ti species (likely Ti 3+ and/or Ti 4+ ). The membrane chemical degradation induced by TiO x is proposed to be due to dissolved ionic Ti species reacting with H 2 O 2 through a Fenton reaction. TiO x is determined to be inviable as electrocatalyst support for PEM fuel cells, and future research is suggested to be directed toward alternative oxides with similar corrosion-resistance.

08 HYDROGEN↗
DOE OSTI2024

Substantial oxygen loss and chemical expansion in lithium-rich layered oxides at moderate delithiation

Delithiation of layered oxide electrodes triggers irreversible oxygen loss, one of the primary degradation modes in lithium-ion batteries. However, the delithiation-dependent mechanisms of oxygen loss remain poorly understood. Here we investigate the oxygen non-stoichiometry in Li 1.18–x Ni 0.21 Mn 0.53 Co 0.08 O 2–δ electrodes as a function of Li content by using cycling protocols with long open-circuit voltage steps at varying states of charge. Surprisingly, we observe substantial oxygen loss even at moderate delithiation, corresponding to 2.5, 4.0 and 7.6 ml O 2 per gram of Li 1.18–x Ni 0.21 Mn 0.53 Co 0.08 O 2–δ after resting at upper capacity cut-offs of 135, 200 and 265 mAh g −1 for 100 h. Our observations suggest an intrinsic oxygen instability consistent with predictions of high oxygen activity at intermediate potentials versus Li/Li + . In addition, we observe a large chemical expansion coefficient with respect to oxygen non-stoichiometry, which is about three times greater than those of classical oxygen-deficient materials such as fluorite and perovskite oxides. Furthermore, our work challenges the conventional wisdom that deep delithiation is a necessary condition for oxygen loss in layered oxide electrodes and highlights the importance of calendar ageing for investigating oxygen stability.

Atomistic models↗