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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 1,027 records · Page 57

Gap states and valley-spin filtering in transition metal dichalcogenide monolayers

The magnetically induced valley-spin filtering in transition metal dichalcogenide monolayers ($\textit{MX}_2$, where $\textit{M}$ = Mo, W and X = S, Se, Te) promises a new paradigm in information processing. However, the detailed understanding of this effect is still limited, regarding its underlying transport processes. As such, herein it is suggested that the filtering mechanism can be greatly elucidated by the concept of metal-induced gap states (MIGS), appearing in the electrode-terminated $\textit{MX}_2$ materials, i.e., the referential filter setup. In particular, the gap states are predicted here to mediate valley- and spin-resolved charge transport near the ideal electrode/$\textit{MX}_2$ interface, and therefore to initiate filtering. It is also argued that the role of MIGS increases when the channel length is diminished, as they begin to govern the overall valley-spin transport in the tunneling regime. In what follows, the presented study yields fundamental scaling trends for the valley-spin selectivity with respect to the intrinsic physics of the filter materials. As a result, it facilitates insight into the analyzed effects and provides design guidelines toward efficient valley-spin filter devices that are based on the discussed materials or other hexagonal monolayers with a broken inversion symmetry.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Secondary electron emission characteristics of molybdenum-masked, ion-textured OFHC copper

A method for producing a uniform, highly textured surface on oxygen-free, high conductivity (OFHC) copper by ion bombardment using sputtered molybdenum as a texture-inducing masking film was developed and used to provide samples for study. The purpose was to develop a basically OFHC copper surface having very low secondary electron emission characteristics. Surfaces having low secondary electron emission are a requirement for the electrodes of very high efficiency multistage depressed collectors (MDC's). Such MDC's are used in microwave amplifier traveling wave tubes for space communications and other applications. OFHC copper is the material most commonly used for MDC electrodes because it has high thermal conductivity, it is easy to machine, and its fabrication and brazing procedures are well established. However, its untreated surface displays relatively very high levels of secondary electron emissions. Textured OFHC copper samples were tested for true secondary electron emission and relative reflected primary electron yield at primary electron beam energy levels from 200 to 2000 eV and at direct (0 deg) to oblique (60 deg) beam impingement angles. The test results for three of the samples, each of which was processed in a slightly different way, are compared with each other and with test results for a machined OFHC copper sample. Although the textured samples are not represented here as having been processed optimally, their measured secondary electron emission characteristics are significantly lower than those of the untreated OFHC copper sample over the range of conditions studied. Importantly, the relative reflected primary electron yield of one of the textured samples is conspicuously lower than that of the others. Clearly, with further development, the molybdenum-masked ion-textured OFHC copper surface will be a promising material for high-efficiency MDC electrodes.

Curren, Arthur N.↗

Designing Low Tortuosity Electrodes through Pattern Optimization for Fast-Charging

The development of fast-charging technologies is crucial for expediting the progress and promotion of electric vehicles. In addition to innovative material exploration, reduction in the tortuosity of electrodes is a favored strategy to enhance the fast-charging capability of lithium-ion batteries by optimizing the ion-transfer kinetics. To realize the industrialization of low-tortuosity electrodes, a facile, cost-effective, highly controlled, and high-output continuous additive manufacturing roll-to-roll screen printing technology is proposed to render customized vertical channels within electrodes. Extremely precise vertical channels are fabricated by applying the as-developed inks, using LiNi 0.6 Mn 0.2 Co 0.2 O 2 as the cathode material. Additionally, the relationship between the electrochemical properties and architecture of the channels, including the pattern, channel diameter, and edge distance between channels, is revealed. The optimized screen-printed electrode exhibited a seven-fold higher charge capacity (72 mAh g -1 ) at a current rate of 6 C and superior stability compared with that of the conventional bar-coated electrode (10 mAh g -1 , 6 C) at a mass loading of 10 mg cm -2 . Finally, this roll-to-roll additive manufacturing can potentially be applied to various active materials printing to reduce electrode tortuosity and enable fast charging in battery manufacturing.

42 ENGINEERING↗

Scalable Freeze-Tape-Casting Fabrication and Pore Structure Analysis of 3D LLZO Solid-State Electrolytes

Nonflammable solid-state electrolytes can potentially address the reliability and energy density limitations of lithium-ion batteries. Garnet-structured oxides such as Li 7 La 3 Zr 2 O 12 (LLZO) are some of the most promising candidates for solid-state devices. Here, three-dimensional (3D) solid-state LLZO frameworks with low tortuosity pore channels are proposed as scaffolds, into which active materials and other components can be infiltrated to make composite electrodes for solid-state batteries. To make the scaffolds, we employed aqueous freeze tape casting (FTC), a scalable and environmentally friendly method to produce porous LLZO structures. Using synchrotron radiation hard X-ray microcomputed tomography, we confirmed that LLZO films with porosities of up to 75% were successfully fabricated from slurries with a relatively wide concentration range. The acicular pore size and shape at different depths of scaffolds were quantified by fitting the pore shapes with ellipses, determining the long and short axes and their ratios, and investigating the equivalent diameter distribution. The results show that relatively homogeneous pore sizes and shapes were sustained over a long range along the thickness of the scaffold. Additionally, these pores had low tortuosity and the wall thickness distributions were found to be highly homogeneous. These are desirable characteristics for 3D solid electrolytes for composite electrodes, in terms of both the ease of active material infiltration and also minimization of Li diffusion distances in electrodes. The advantages of the FTC scaffolds are demonstrated by the improved conductivity of LLZO scaffolds infiltrated with poly(ethylene oxide)/lithium bis(trifluoromethanesulfonyl)imide (PEO/LITFSI) compared to those of PEO/LiTFSI films alone or composites containing LLZO particles.

36 MATERIALS SCIENCE↗

Methods—Kintsugi Imaging of Battery Electrodes: Distinguishing Pores from the Carbon Binder Domain using Pt Deposition

The mesostructure of porous electrodes used in lithium-ion batteries strongly influences cell performance. Accurate imaging of the distribution of phases in these electrodes would allow this relationship to be better understood through simulation. However, imaging the nanoscale features in these components is challenging. While scanning electron microscopy is able to achieve the required resolution, it has well established difficulties imaging porous media. This is because the flat imaging planes prepared using focused ion beam milling will intersect with the pores, which makes the images hard to interpret as the inside walls of the pores are observed. It is common to infiltrate porous media with resin prior to imaging to help resolve this issue, but both the nanoscale porosity and the chemical similarity of the resins to the battery materials undermine the utility of this approach for most electrodes. In this study, a technique is demonstrated which uses in situ infiltration of platinum to fill the pores and thus enhance their contrast during imaging. Reminiscent of the Japanese art of repairing cracked ceramics with precious metals, this technique is referred to as the kintsugi method. The images resulting from applying this technique to a conventional porous cathode are presented and then segmented using a multi-channel convolutional method. We show that while some cracks in active material particles were empty, others appear to be filled (perhaps with the carbon binder phase), which will have implications for the rate performance of the cell. Energy dispersive X-ray spectroscopy was used to validate the distribution of phases resulting from image analysis, which also suggested a graded distribution of the binder relative to the carbon additive. The equipment required to use the kintsugi method is commonly available in major research facilities and so we hope that this method will be rapidly adopted to improve the imaging of electrode materials and porous media in general.

25 ENERGY STORAGE↗

Rheological and microstructural characterization of aqueous suspensions of carbon black and reduced graphene oxide

Carbon black is often used as a conductivity enhancer in battery electrodes. Reduced graphene oxide is another conducting material, with a high aspect ratio sheet-like morphology, and offers the possibility of generating a conducting network at loadings that are small compared to carbon black. Suspensions of conducting carbon, active materials and binders are typically coated on current collectors during the formation of electrodes. The rheology of these suspensions is an important indicator of the connectivity of particles in the suspension and impacts the electrical conductivity as well as the thickness of the coated layer. In this work, the rheology and microstructures of aqueous suspensions of para-aminobenzoic acid terminated carbon black (CB) with and without reduced graphene oxide (RGO) were investigated. The CB loading varied between 0.05 wt.% -10 wt.%, while the samples containing RGO had an RGO loading of 0.05 wt.%. The pH of the suspension was varied from 7.5 to 3. The carboxyl groups on the CB surface are deprotonated at pH 7.5, making the particles hydrophilic. Protonation of the carboxylate groups at pH 3 makes the particles partially hydrophobic. Suspensions of CB showed Newtonian behavior at all loadings for pH 7.5, and at loadings below 1.5 wt.% for pH 3. They are shear thinning at loadings between 1.5–10 wt.%. Interestingly, the low shear viscosity is non-monotonic with CB loading, rising up to a CB loading of 7.5 wt.%, and then dropping at 10 wt.%. Cryogenic scanning electron microscopy (SEM) showed CB particles forming aggregates at pH 3 for CB loadings greater than 1.5 wt.%. At pH 3, addition of 0.05 wt.% RGO resulted in a viscosity increase for suspensions containing 0.5 wt.% CB, as the RGO formed connections with CB particles that enhanced network formation. Adding RGO had little effect on suspensions that had 1.5 wt.% CB. The combination of SEM imaging and suspension rheology provides insight into the particle connectivity for the carbon-based materials studied here. These insights will be useful in determining coating conditions for slurries used in rechargeable battery electrodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Graphene monoxide compositions of matter and electrodes comprising them

A composition of graphene-based nanomaterials characterized by at least one area of one atomic layer of graphene monoxide, wherein at least a portion of oxygen molecules present in the graphene monoxide are incorporated into specific crystalline structural moieties, methods of making the same, electrodes in electrochemical devices incorporating the same, and compositions of lithium and graphene monoxide containing materials that result from cycling said electrodes.

Hirschmugl, Carol J.↗

Electrochemical generation of carbon-containing products from carbon dioxide and carbon monoxide

Disclosed herein is a method of electroreduction with a working electrode and counter electrode. The method includes a step of electrocatalyzing carbon monoxide and/or carbon dioxide in the presence of one or more nucleophilic co-reactants in contact with a catalytically active material present on the working electrode, thereby forming one or more carbon-containing products electrocatalytically.

Jiao, Feng↗

A High-Energy NASICON-Type Cathode Material for Na-Ion Batteries

Over the last decade, Na-ion batteries have been extensively studied as low-cost alternatives to Li-ion batteries for large-scale grid storage applications; however, the development of high-energy positive electrodes remains a major challenge. Materials with a polyanionic framework, such as Na superionic conductor (NASICON)-structured cathodes with formula Na x M 2 (PO 4 ) 3 , have attracted considerable attention because of their stable 3D crystal structure and high operating potential. Herein, a novel NASICON-type compound, Na 4 MnCr(PO 4 ) 3 , is reported as a promising cathode material for Na-ion batteries that deliver a high specific capacity of 130 mAh g –1 during discharge utilizing high-voltage Mn 2+/3+ (3.5 V), Mn 3+/4+ (4.0 V), and Cr 3+/4+ (4.35 V) transition metal redox. In addition, Na 4 MnCr(PO 4 ) 3 exhibits a high rate capability (97 mAh g –1 at 5 C) and excellent all-temperature performance. In situ X-ray diffraction and synchrotron X-ray diffraction analyses reveal reversible structural evolution for both charge and discharge.

25 ENERGY STORAGE↗

Progress in Development of Improved Ion-Channel Biosensors

Further improvements have recently been made in the development of the devices described in Improved Ion-Channel Biosensors (NPO-30710), NASA Tech Briefs, Vol. 28, No. 10 (October 2004), page 30. As discussed in more detail in that article, these sensors offer advantages of greater stability, greater lifetime, and individual electrical addressability, relative to prior ion-channel biosensors. In order to give meaning to a brief description of the recent improvements, it is necessary to recapitulate a substantial portion of the text of the cited previous article. The figure depicts one sensor that incorporates the recent improvements, and can be helpful in understanding the recapitulated text, which follows: These sensors are microfabricated from silicon and other materials compatible with silicon. Typically, the sensors are fabricated in arrays in silicon wafers on glass plates. Each sensor in the array can be individually electrically addressed, without interference with its neighbors. Each sensor includes a well covered by a thin layer of silicon nitride, in which is made a pinhole for the formation of a lipid bilayer membrane. In one stage of fabrication, the lower half of the well is filled with agarose, which is allowed to harden. Then the upper half of the well is filled with a liquid electrolyte (which thereafter remains liquid) and a lipid bilayer is painted over the pinhole. The liquid contains a protein that forms an ion channel on top of the hardened agarose. The combination of enclosure in the well and support by the hardened agarose provides the stability needed to keep the membrane functional for times as long as days or even weeks. An electrode above the well, another electrode below the well, and all the materials between the electrodes together constitute a capacitor. What is measured is the capacitive transient current in response to an applied voltage pulse. One notable feature of this sensor, in comparison with prior such sensors, is a relatively thick dielectric layer between the top of the well and the top electrode. This layer greatly reduces the capacitance of an aperture across which the ion channels are formed, thereby increasing the signal-to-noise ratio. The use of a relatively large aperture with agarose support makes it possible to form many ion channels instead of only one, thereby further increasing the signal-to-noise ratio and effectively increasing the size of the available ionic reservoir. The relatively large reservoir makes it possible to measure AC rather than DC. This concludes the recapitulation from the cited previous article.

Nadeau, Jay L.↗

From Materials to Cell: State-of-the-Art and Prospective Technologies for Lithium-Ion Battery Electrode Processing

Electrode processing plays an important role in advancing lithium-ion battery technologies and has a significant impact on cell energy density, manufacturing cost, and throughput. Compared to the extensive research on materials development, however, there has been much less effort in this area. In this Review, we outline each step in the electrode processing of lithium-ion batteries from materials to cell assembly, summarize the recent progress in individual steps, deconvolute the interplays between those steps, discuss the underlying constraints, and share some prospective technologies. Finally, this Review aims to provide an overview of the whole process in lithium-ion battery fabrication from powder to cell formation and bridge the gap between academic development and industrial manufacturing.

25 ENERGY STORAGE↗

Development of an All-Metal Thick Film Cost Effective Metallization System for Solar Cells

Materials including copper powders, silver-fluoride, and silicon wafers were procured and copper pastes were prepared. Electrodes made with copper pastes were analyzed and compared with the raw materials. A needle-like structure was observed on the electroded solar cells, and was identified as eutectic copper-silicon by electron probe X-ray spectroscopy. The existence of this phase was thought to benefit electrical and metallurgical properties of the contact. Subsequently electrodes made from new material were also shown to contain this phase while simultaneously having poor adhesion.

Ross, B.↗

Long Life Nickel Electrodes for Nickel-Hydrogen Cells: Fiber Substrates Nickel Electrodes

Samples of nickel fiber mat electrodes were investigated over a wide range of fiber diameters, electrode thickness, porosity and active material loading levels. Thickness' were 0.040, 0.060 and 0.080 inches for the plaque: fiber diameters were primarily 2, 4, and 8 micron and porosity was 85, 90, and 95%. Capacities of 3.5 in. diameter electrodes were determined in the flooded condition with both 26 and 31% potassium hydroxide solution. These capacity tests indicated that the highest capacities per unit weight were obtained at the 90% porosity level with a 4 micron diameter fiber plaque. It appeared that the thinner electrodes had somewhat better performance, consistent with sintered electrode history. Limited testing with two-positive-electrode boiler plate cells was also carried out. Considerable difficulty with constructing the cells was encountered with short circuits the major problem. Nevertheless, four cells were tested. The cell with 95% porosity electrodes failed during conditioning cycling due to high voltage during charge. Discharge showed that this cell had lost nearly all of its capacity. The other three cells after 20 conditioning cycles showed capacities consistent with the flooded capacities of the electrodes. Positive electrodes made from fiber substrates may well show a weight advantage of standard sintered electrodes, but need considerably more work to prove this statement. A major problem to be investigated is the lower strength of the substrate compared to standard sintered electrodes. Problems with welding of leads were significant and implications that the electrodes would expand more than sintered electrodes need to be investigated. Loading levels were lower than had been expected based on sintered electrode experiences and the lower loading led to lower capacity values. However, lower loading causes less expansion and contraction during cycling so that stress on the substrate is reduced.

Rogers, Howard H.↗

Low power arcjet life issues

The present evaluation of the results of arcjet engine lifetime testing attempts to deepen understanding of the electrode erosion process, with a view to its minimization. Attention is given to the compatibility of materials with N2H4, the dependence of electrode erosion on geometry and flow field, and the erosive effects associated with the arcjet power supply. Results are presented for thrusters employing either decomposed N2H4 or cold mixed gases, over a power range of 900 to 2000 W.

Simon, M. A.↗

EFRC Accomplishments 2014-2020: NorthEast Center for Chemical Energy Storage (NECCES)

The mission of NECCES is to develop an understanding of how key electrode reactions occur in cathode materials for Li based batteries, and how they can be controlled to improve electrochemical performance, from the atomistic level to the macroscopic level through the life-time of the operating battery. This mission will allow the determination of the ultimate limits of intercalation reactions for chemical energy storage. The approach and specific research goals of NECCES are to: 1. Attain reversible multi-electron transfer in a cathode material using lithium, using the model compound ε -VOPO 4 ; 2. Close the gap between the theoretical and practical energy density for intercalation compounds, using the model compound LiNi 0.85 Co 0 .10Al 0.05 O 2 ; 3. Understand the transition from cation redox to anion redox electrochemistry; 4. Understand performance limiting transport in positive electrode structures from the local through the meso to the macroscale.

25 ENERGY STORAGE↗

Roll-To-Roll Atomic Layer Deposition of Titania Nanocoating on Thermally Stabilizing Lithium Nickel Cobalt Manganese Oxide Cathodes for Lithium Ion Batteries

Conformal coating of ceramic layers (nm-thick) on Ni-rich layered cathode materials is an effective strategy for improving high-temperature longevity of Li-ion batteries (LIBs). In this work, we develop a roll-to-roll atomic layer deposition (R2R ALD) apparatus for growing uniform nanolayers of TiO 2 . We explore the effect of ALD parameters (temperature: 120–180 °C and line speed: 2–40 mm s –1 ) on the TiO 2 surface coating and subsequently investigate the electrochemical performance of the as-prepared cathodes. The capacity retention of TiO 2 -coated porous electrodes is substantially improved compared to that of the pristine cathode material for high-temperature cycling. Electrochemical impedance spectroscopy confirms that the ALD-TiO 2 coating suppresses the undesired side reactions initiated at the electrode/electrolyte interface, reduces charge transfer resistance, and ultimately facilitates the Li + transport through the composite cathode nanostructure. The robust design of the ALD-TiO 2 cathode material enables high-temperature operation (>55 °C) with enhanced specific capacity, superior rate capability, excellent cyclability, and ultra-high coulombic efficiency within a wide potential window (3.0–4.35 V). Furthermore, the R2R ALD technique developed in this work paves the way for large-scale fabrication of ceramic-coated cathode sheets with a production rate reaching 2.4 m min –1 for a continuous coating operation.

25 ENERGY STORAGE↗

Dielectrophoresis-based particle sensor using nanoelectrode arrays

A method for concentrating or partly separating particles of a selected species from a liquid or fluid containing these particles and flowing in a channel, and for determining if the selected species particle is present in the liquid or fluid. A time varying electrical field E, having a root-mean-square intensity E.sup.2.sub.rms with a non-zero gradient in a direction transverse to the liquid or fluid flow direction, is produced by a nanostructure electrode array, with a very high magnitude gradient near exposed electrode tips. A dielectrophoresis force causes the selected particles to accumulate near the electrode tips, if the medium and selected particles have substantially different dielectric constants. An insulating material surrounds most of each of the nanostructure electrodes, and a region of the insulating material surface is functionalized to promote attachment of the selected species particles to the surface. An electrical property value Z(meas) is measured at the functionalized surface and is compared with a reference value Z(ref) to determine if the selected species particles are attached to the functionalized surface.

Li, Jun↗