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At least 1,765 records · Page 98

An aerothermodynamic study of slender conical vehicles

A numerical study was performed to assess the applicability of some current techniques which can be used for aerothermal predictions over slender spherically blunted cones. Predictions using a viscous-shock-layer method and several engineering approaches were compared with experimental results from flight and ground-based tests, with each other, and with other detailed results. Good agreement was obtained in comparisons with laminar and turbulent heating data from the Reentry F flight vehicle and with the wind-tunnel data. In particular, the viscous-shock-layer method was shown to yield excellent comparisons and should be useful in providing detailed flowfield and surface values for slender blunted cones. Additional predictions were obtained with these methods for two 5-deg half-angle cones with different nose radii to illustrate the effects of nose bluntness and angle of attack on drag and heat transfer. These results demonstrate the benefit of nose blunting with respect to heating and drag for laminar and transitional flow at zero-lift conditions and the benefit of heating reduction at angle of attack. Detailed comparison of the engineering code predictions with the viscous-shock-layer results for these additional cases generally showed good agreement except for the laminar prodictions at angle of attack on the forward cone surface. Nonequilibrium calculations at 0-deg angle of attack showed that substantial benefits of low surface catalysis existed only in the nose-dominated region.

Thompson, R. A.↗

Summary of aerothermal test results from the first flight of the Pegasus air-launched space booster

Temperature measurements were obtained on the Pegasus booster from launch through Mach 8.0. The majority of sensors were thin-foil temperature gages installed near the surface within the vehicle's ablating thermal protection system. These gages were distributed on the wing surfaces and on the wing-body fairing or fillet. Temperature time histories from these installations are presented. In addition, thermocouples were installed on the surface of nonablating plugs located on the fairing. These sensors were more responsive to changes in flight conditions than the foil gages and allowed a derivation of convective heat flux. A heating rate magnification of 2 was found in the vicinity of the wing shock interaction.

Noffz, Gregory K.↗

Thin Film Sensors for Fission Surface Power

Physical sensors fabricated with thin films could result a significant savings in space and weight with improved reliability for monitoring the long-term operation of fission surface power systems. Thin film sensors of 1 µm or less are attractive for FSP applications because they can be incorporated onto component surfaces with minimal machining and the additional weight to a system is minimal compared to thick film-, wire-, or foil-based sensors. The thin, surface fabrication of the sensors is also expected to make them less susceptible to deep dose effects that affect thicker sensors. An overview of thin film sensors using thermocouples and resistive elements designed, fabricated, and demonstrated at GRC for aerospace applications exceeding 900°C is presented.

Fission Surface Power↗

Effect of dielectric target properties on plasma surface ionization wave propagation

Surface ionization waves (SIWs) propagating along dielectric covered, grounded surfaces have been studied for various dielectric bulk and surface conditions; a dependence on the propagation velocity with respect to dielectric electrical thickness and near surface permittivity profiles are observed. SIWs generated by an atmospheric pressure plasma source are imaged interacting with planar dielectric surface. Surface wave velocity is obtained by tracking emission intensity as a function of time. Target dielectric thickness is varied from $d = 0.15-10$ mm and dielectric constant is varied from $\epsilon_r = 6.21 - 9.4$. The propagation of SIWs can be generally predicted by relating their velocity to the RC time constant of the circuit generated between the plasma and the dielectric surface, but it is found that this approximation breaks down for dielectric substrates of sufficient thickness and wave velocity becomes constant. The results show that wave velocity is stable and predictable for target thicknesses beyond a certain point determined by the permittivity of the target material. It is also shown that SIW propagation is strongly driven by the dielectric material near to the surface of the target in addition to the bulk material. The possible mechanisms driving these thickness dependent behaviors is discussed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Minimizing distortion in truss structures via Tabu search

The shape control of large flexible space structures is of great interest to structural designers. A related problem is to seek ways to minimize the need for active controls by careful design and construction of the space structure. A tetrahedral truss structure that is used to support a precision segmented reflector or antenna surface is considered. The structure has a hexagonal platform and is characterized by the number of rings of members in the truss. For simplicity it is assumed that a flat truss geometry exists. Hence, all structural members and ball joints are required to have the same nominal length and diameter, respectively. Inaccuracies in the length of member or diameters of joints may produce unacceptable levels of surface distortion and internal forces. In the case of a truss structure supporting an antenna, surface distortions may cause unacceptable gain loss or pointing errors. The focus is solely on surface distortion, however, internal forces may be treated in a similar manner. To test the Tabu search code for DSQRMS the appropriate influence matrices are used for a flat, two-ring tetrahedral reflector truss generated by Green and Haftka (1989). In this example there are 102 members (NMEMB) and 31 ball joints (NJOINT) of the same nominal length, respectively. Hence, all the members may be interchanged and all the joints may be interchanged. In addition, 19 positions on the surface of the truss (NNODES) were used to measure error influences. After a variety of experiments a set of good parameters was choosen for Tabu search. The sample size at each iteration is 10*NMEMB and the short term memory size is 40. In addition four pruning rules were used to accelerate the search..

Kincaid, Rex K.↗

Fermi-crossing Type-II Dirac fermions and topological surface states in NiTe 2

Transition-metal dichalcogenides (TMDs) offer an ideal platform to experimentally realize Dirac fermions. However, typically these exotic quasiparticles are located far away from the Fermi level, limiting the contribution of Dirac-like carriers to the transport properties. Here we show that NiTe 2 hosts both bulk Type-II Dirac points and topological surface states. The underlying mechanism is shared with other TMDs and based on the generic topological character of the Te p-orbital manifold. However, unique to NiTe 2 , a significant contribution of Ni d orbital states shifts the energy of the Type-II Dirac point close to the Fermi level. In addition, one of the topological surface states intersects the Fermi energy and exhibits a remarkably large spin splitting of 120 meV. Our results establish NiTe 2 as an exciting candidate for next-generation spintronics devices.

36 MATERIALS SCIENCE↗

Dynamic Restructuring Induced Oxygen Activation on AgCu Near Surface Alloys

Recent studies have shown that the addition of Cu to Ag catalysts improves their epoxidation performance by increasing the overall selectivity of the bimetallic catalyst. We have prepared AgCu near-surface alloys and used scanning tunneling microscopy to gain an atomistic picture of O 2 dissociation on the bimetallic system. These data reveal a higher dissociative sticking probability for O 2 on AgCu than Ag(111), and density functional theory (DFT) confirms that the O 2 dissociation barrier is 0.17 eV lower on the alloy. Surprisingly, we find that after a slow initial uptake of O 2 , the sticking probability increases exponentially. Further DFT calculations indicate that surface oxygen reverses the segregation energy for AgCu, stabilizing Cu atoms in the Ag layer. These single Cu atoms in the Ag surface are found to significantly lower the O 2 dissociation barrier. Altogether, these results explain nonlinear effects in the activation of O 2 on this catalytically relevant surface alloy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tensile properties of ADI material in water and gaseous environments

Austempered ductile iron (ADI) is an advanced type of heat treated ductile iron, having comparable mechanical properties as forged steels. However, it was found that in contact with water the mechanical properties of austempered ductile irons decrease, especially their ductility. Despite considerable scientific attention, the cause of this phenomenon remains unclear. Some authors suggested that hydrogen or small atom chemisorption causes the weakening of the surface atomic bonds. To get additional reliable data of that phenomenon, in this paper, two different types of austempered ductile irons were tensile tested in various environments, such as: argon, helium, hydrogen gas and water. It was found that only the hydrogen gas and water gave a statistically significant decrease in mechanical properties, i.e. cause embrittlement. Furthermore, the fracture surface analysis revealed that the morphology of the embrittled zone near the specimen surface shares similarities to the fatigue micro-containing striation-like lines, which indicates that the morphology of the brittle zone may be caused by cyclic local-chemisorption, micro-embrittlement and local-fracture. - Highlights: • In contact with water and other liquids the ADI suddenly exhibits embrittlement. • The embrittlement is more pronounced in water than in the gaseous hydrogen. • The hydrogen chemisorption into ADI surface causes the formation of a brittle zone. • The ADI austempered at lower temperatures (300 °C) is more resistant to embrittlement.

36 MATERIALS SCIENCE↗

Alpha Shape Analysis (ASA) Framework for Post- Clustering Property Determination in Atom Probe Tomographic Data

While application of clustering algorithms to atom probe tomography data have enabled quantification of solute clusters in terms of number density, size, and subcomposition there exist other properties (e.g., volume, surface area, and composition) that are better determined by defining an interface between the cluster and the surrounding matrix. The limitation in composition results from an ion selection step where the expected matrix ion types are omitted from the cluster search algorithm to enhance the contrast between the matrix and cluster and to reduce the complexity of the search. Previously, composition determination within solute clusters has utilized a secondary envelopment and erosion step on top of conventional methods such as maximum separation. In this work, we present a novel stochastic method that combines the particle identification fidelity of a conventional clustering algorithm with the analytical flexibility of mesh-based approaches through the generation of alpha shapes for each identified cluster. Furthermore, the corresponding mesh accounts for concave components of the clusters and determines the volume and surface area of the clusters; additionally, the mesh boundary is utilized to update the total composition according to the internal ions.

42 ENGINEERING↗

Atomic oxygen density determination in the effluent of the COST reference source using in situ effective lifetime measurements in the presence of a liquid interface

Abstract Spatially resolved, absolute densities of atomic oxygen are measured for several helium-based admixtures in the effluent of the COST Reference Microplasma Jet using two-photon absorption laser induced fluorescence (TALIF). Admixtures investigated include a helium-only admixture, four helium/oxygen admixtures (0.1 % , 0.5 % , 0.6 % , and 1.0 % oxygen), and a helium/water admixture (2500 ppm water), chosen to coincide with previously published characterizations of plasma-treated liquid. The atomic oxygen TALIF signal is calibrated for density using the noble gas xenon, which possesses a very similar two-photon excitation and fluorescence scheme. Measurements are conducted for the jet operating in ambient air with both an open effluent and a liquid surface present, allowing for comparison with liquid phase measurements conducted under similar conditions. The presence of a water surface does not appear to alter the background chemistry in the effluent but reduces O densities close to the liquid interface when compared to a similar distance from the nozzle in an open effluent case. This may be the result of a reduction in flow velocity caused by the liquid obstructing the gas flow. Additionally, measurements near the liquid surface revealed a region of atomic oxygen well outside of where the core of the effluent impinges on the liquid. This is likely relevant for applications as it considerably expands the surface area subject to O absorption. Critically, in situ measurements of the effective lifetimes of the laser-excited 3p 3 P J state of atomic oxygen were recorded in the effluent by employing a picosecond (ps) laser and a nanosecond (ns) ICCD. By experimentally determining the contribution from collisional quenching via the in situ effective lifetime measurements, significant improvements in the accuracy of the atomic oxygen density calibration were made, with differences of approximately 30 % from existing methods of estimating quenching rates at atmospheric pressure. Finally, spatially resolved atomic oxygen densities allow for an investigation of O formation and extinction pathways in the effluent and a comparison between admixtures.

laser diagnostics↗

Infrared thermal mapping of the Martian surface and atmosphere - First results

The Viking infrared thermal mapper measures the thermal emission of the Martian surface and atmosphere and the total reflected sunlight. With the high resolution and dense coverage being achieved, planetwide thermal structure is apparent at large and small scales. The thermal behavior of the best-observed areas, the landing sites, cannot be explained by simple homogeneous models. The data contain clear indications for the relevance of additional factors such as detailed surface texture and the occurrence of clouds. Areas in the polar night have temperatures distinctly lower than the CO2 condensation point at the surface pressure. This observation implies that the annual atmospheric condensation is less than previously assumed and that either thick CO2 clouds exist at the 20-kilometer level or that the polar atmosphere is locally enriched by noncondensable gases.

Kieffer, H. H.↗

Primary Volatile Abundances in Comets from Infrared Spectroscopy: Implications for Reactions on Grain Surfaces in the Interstellar/Nebular Environment

Comets retain relatively primitive icy material remaining from the epoch of Solar System formation, however the extent to which they are modified from their initial state remains a key question in cometary science. High-resolution lR spectroscopy has emerged as a powerful tool for measuring vibrational emissions from primary volatiles (i.e., those contained in the nuclei of comets). With modern instrumentation, most notably NIRSPEC at the Keck II 10-m telescope, we can quantify species of astrobiological importance (e.g., H20, C2H2, CH4, C2H6, CO, H2CO, CH30H, HCN, NH3). In space environments, compounds of keen interest to astrobiology could originate from HCN and NH3 (leading to amino acids), H2CO (leading to sugars), or C2H6 and CH4 (suggested precursors of ethyl- and methylamine). Measuring the abundances of these precursor molecules (and their variability among comets) is a feasible task that contributes to understanding their delivery to Earth's early biosphere and to the synthesis of more complex pre biotic compounds. Over 20 comets have now been measured with IR spectroscopy, and this sample reveals significant diversity in primary volatile compositions. From this, a taxonomic classification scheme is emerging, presumably reflecting the diverse conditions experienced by pre-cometary grains in interstellar and subsequent nebular environs. The importance of H-atom addition to C2H2 on the surfaces of interstellar grains to produce C2H6 was validated by the discovery of abundant ethane in comet C/1996 B2 (Hyakutake) with C2H6/CH4 well above that achievable by gas-phase chemistry , and then in irradiation experiments on laboratory ices at 10 - 50 K. The large abundance ratios C2H6/CH4 observed universally in comets establish H-atom addition as an important and likely ubiquitous process, and comparing C2H6/C2H2 among comets can provide information on its efficiency. The IR is uniquely capable since symmetric hydrocarbons (e.g., C2H2, CH4, C2H6) have no electric dipole moment and thus no allowed pure rotational transitions. CO should also be hydrogenated on grain surfaces. Irradiation experiments on interstellar ice analogs show this to require very low temperatures, the resulting yields of H2CO and CH30H being highly dependent on temperature in the range approx 10 - 25 K. The relative abundances of these chemically-related molecules in comets provide one measure of the efficiency of H-atom addition to CO Oxidation of CO is also important on grain mantles, as evidenced by the widespread presence of C02 ice towards interstellar sources observed with ISO and in a survey of 17 comets observed with AKARI. H-atom addition to C2H2 produces the vinyl radical, and through subsequent oxidation1reduction reactions can lead to vinyl alcohol, acetaldehyde, and ethanol This may have implications for interpreting observed abundance ratios CO/C2H2. We will discuss possible implications regarding formation conditions in the context of measured primary volatile compositions, emphasizing recently observed comets and published results. These are continually providing new insights regarding our taxonomic scheme and also delivery of pre-biological material to the young Earth.

DiSanti, M. A.↗

An Updated Global Grid Point Surface Air Temperature Anomaly Data Set: 1851-1990 (revised 1991) (NDP-020)

This NDP presents land-based monthly surface-air-temperature anomalies (departures from a 1951-1970 reference period mean) on a 5° latitude by 10° longitude global grid. Monthly surface-air-temperature anomalies (departures from a 1957-1975 reference period mean) for the Antarctic (grid points from 65°S to 85°S) are presented in a similar way as a separate data set. The data were derived primarily from the World Weather Records and from the archives of the United Kingdom Meteorological Office. This long-term record of temperature anomalies may be used in studies addressing possible greenhouse-gas-induced climate changes. To date, the data have been employed in producing regional, hemispheric, and global time series for determining whether recent (i.e., post-1900) warming trends have taken place. The present updated version of this data set is identical to the earlier version for all records from 1851-1978 except for the addition of the Antarctic surface-air-temperature anomalies beginning in 1957. Beginning with the 1979 data, this package differs from the earlier version in several ways. Erroneous data for some sites have been corrected after a review of the actual station temperature data, and inconsistencies in the representation of missing values have been removed. For some grid locations, data have been added from stations that had not contributed to the original set. Data from satellites have also been used to correct station records where large discrepancies were evident. The present package also extends the record by adding monthly surface-air-temperature anomalies for the Northern (grid points from 85°N to 0°) and Southern (grid points from 5°S to 60°S) Hemispheres for 1985-1990. In addition, this updated package presents the monthly-mean-temperature records for the individual stations that were used to produce the set of gridded anomalies. The periods of record vary by station. Northern Hemisphere data have been corrected for inhomogeneities, while Southern Hemisphere data are presented in uncorrected form.For access to the data files, click this link to the CDIAC data transition website: http://cdiac.ess-dive.lbl.gov/ndps/ndp020.html

54 ENVIRONMENTAL SCIENCES↗

Application and Use of Lunar Node-Derived Beacons for Lunar Surface Navigation

To maximize the scientific return and safety of operations on the lunar surface, multiple civil organizations are investing in Position, Navigation, and Timing infrastructure. This approach mimics the deployment of Global Navigation Satellite Systems around the Earth and aims to enable a similar robust capability around the moon. With these satellites, it will be possible to maintain high- fidelity knowledge of positioning and timing both on the surface and in orbit. For initial deployments, this capability is focused on high need areas, such as the Lunar South Pole, the target of the currently in-planning Artemis surface missions to high accuracy. Similar to GNSS systems, this capability will be implemented over time to build up to a level of global access for real-time navigation. For early missions, this means a limited capability in terms of coverage. To provide increased performance, ground augmentation can be leveraged. This not only provides an additional reference signal but helps to supply timing to enable a high accuracy real-time position solutions. This paper discusses the path towards evolving the Lunar Node 1 platform to augment these early constellation deployments. Analysis of notional performance with and without surface aids is provided, as well as discussion and paths towards deployment and operation. Given the analysis results, the benefit of surface navigation aids to both provide additional surface-based signals to fill in coverage gaps helps to provide additional robustness and an early-on capability.

Evan J. Anzalone↗

Mars Ascent Vehicle-Propellant Aging

This project is to develop and test a new propellant formulation specifically for the Mars Ascent Vehicle (MAV) for the robotic Mars Sample Return mission. The project was initiated under the Planetary Sciences Division In-Space Propulsion Technology (ISPT) program and is continuing under the Mars Exploration Program. The two-stage, solid motor-based MAV has been the leading MAV solution for more than a decade. Additional studies show promise for alternative technologies including hybrid and bipropellant options, but the solid motor design has significant propellant density advantages well suited for physical constraints imposed while using the SkyCrane descent stage. The solid motor concept has lower specific impulse (Isp) than alternatives, but if the first stage and payload remain sufficiently small, the two-stage solid MAV represents a potential low risk approach to meet the mission needs. As the need date for the MAV slips, opportunities exist to advance technology with high on-ramp potential. The baseline propellant for the MAV is currently the carboxyl terminated polybutadiene (CTPB) based formulation TP-H-3062 due to its advantageous low temperature mechanical properties and flight heritage. However, the flight heritage is limited and outside the environments, the MAV must endure. The ISPT program competed a propellant formulation project with industry and selected ATK to develop a new propellant formulation specifically for the MAV application. Working with ATK, a large number of propellant formulations were assessed to either increase performance of a CTPB propellant or improve the low temperature mechanical properties of a hydroxyl terminated polybutadiene (HTPB) propellant. Both propellants demonstrated potential to increase performance over heritage options, but an HTPB propellant formulation, TP-H-3544, was selected for production and testing. The test plan includes propellant aging first at high vacuum conditions, representative of the Mars transit, followed by an additional year at simulated Mars surface conditions. The actual Mars surface environment is based on the igloo design, actively maintains the propellant at or above -40 degC, 95% carbon dioxide at Mars surface pressure. The NASA Marshall Space Flight Center (MSFC) Mars environment test facility is shown in figure 1 and located in the East Test area of Redstone Arsenal due to storage of live propellants. The facility consists of a vacuum chamber placed inside a large freezer unit. The facility includes pressure and temperature monitoring equipment in addition to a vacuum quality monitoring system spectrometer to record any outgassing products.

Dankanich, John↗

Features of photoconversion in highly efficient silicon solar cells

The photoconversion efficiency η in highly efficient silicon-based solar cells (SCs) is analyzed depending on the total surface-recombination rate S{sub s} on illuminated and rear surfaces. Solar cells based on silicon p-n junctions and α-Si:H or α-SiC:H-Si heterojunctions (so-called HIT structures) are considered in a unified approach. It is shown that a common feature of these SCs is an increased open-circuit voltage V{sub oc} associated with an additional contribution of the rear surface. Within an approach based on analysis of the physical features of photoconversion in SCs, taking into account the main recombination mechanisms, including Shockley-Read-Hall recombination, radiative recombination, surface recombination, recombination in the space-charge region, and band-to-band Auger recombination, expressions for the photoconversion efficiency of such SCs are obtained. The developed theory is compared with experiments, including those for SCs with record parameters, e.g., η = 25% and 24.7% for SCs with a p-n junction for HIT structures, respectively, under AM1.5 conditions. By comparing theory and experiment, the values of S{sub s} achieved as a result of recombination-loss minimization by various methods are determined. The results of calculations of the maximum possible value η{sub max} in silicon SCs are compared with the data of other papers. Good agreement is observed.

30 DIRECT ENERGY CONVERSION↗

SERS Theory: The Chemical Effect of Rhodamine 6G Adsorption on Silver Surfaces on Its Raman Spectrum

The SERS spectra of small organic molecules can be very sensitive to the physisorption or chemisorption of the molecules onto metallic surfaces. However it is challenging to model the results, as typical SERS substrates have a broad distribution of possible surface sites, and the populations of these sites and the SERS enhancement factors associated with them are very difficult to determine, especially when electromagnetic hot spots dominate the observed spectra. However it is important to account for these effects if one is to make a quantitative interpretation of measured SERS spectra. Indeed, the influence of different sites is important to both the electromagnetic and chemical mechanisms in SERS, where the former mechanism is concerned with local field enhancement effects arising from plasmon excitation, while the latter arises from the effect of chemisorption induced charged transfer on the Raman intensities, as can be modeled using static limit Raman intensity calculations[1]. Extensive studies have been performed on simple organics like pyridine bound to gold and silver clusters, and it was found that both the chemical and electrodynamic enhancement factors associated with binding pyridine in various orientations result in noticeable changes in the SERS spectra compared to the gas phase spectrum of pyridine.[2] One of the most important benchmark molecules for SERS and TERS studies is Rhodamine 6G (R6G). This is a strongly fluorescent dye molecule in solution, but when adsorbed onto SERS substrates, its fluorescence is quenched, and the resulting SERS intensities are among the largest observed for any molecule. As a result R6G has played a crucial role in the development of single molecule SERS, and in the development of SERS substrates. [3, 4] Previously, the SERS spectrum of R6G has been modeled as if it were a gas phase molecule. Jensen and Schatz[5] incorporated resonant effects as well as vibronic effects and found that resonance excitation to the S1 excited state of R6G resulted in good agreement with spectra obtained from SERS experiments. In another study, intermolecular charge transfer was studied with R6G bound to a Ag2 cluster.[6] It is unclear if a cluster model as small as two silver atoms can accurately capture the surface effects of a nanoparticle with thousands of atoms. Recent single molecule, ultra high vacuum, tip enhanced Raman spectroscopy (SM-UHV-TERS) measurements for R6G[3] were moderately reproduced by gas phase resonance Raman calculations. Of particular importance in this work was the comparison of TERS spectra at room temperature with those at a low temperature of 10K. It was found that lowering the temperature led to both sharpening of the vibrational spectra, and shifts in the spectra (up to 20 cm-1 with some lines shifting red, some blue and some not at all), suggesting that the molecule transitions from a largely gas phase molecule at room temperature to being strongly chemisorbed at 10K. A potential energy distribution analysis performed by Chulhai and Jensen[3] showed that the modes that were shifted from the gas phase had vibrational activity associated with the ethylamine component of R6G, which is the likely moiety associated with Raman calculations. What remains unresolved concerning the SM-UHV-TERS studies of R6G is direct evidence that the chemical binding of R6G to a silver nanoparticle surfaces causes frequency shifts and/or intensity changes in the Raman scattering intensities of specific modes, especially those involving vibrations of the ethylamine moiety. The theoretical work described in this chapter directly addresses this issue by calculating Raman spectra for R6G interacting with a 20-atom silver cluster, and with a flat Ag(111) surface. Tetrahedral Ag20 is chosen for part of these studies as it provides a model nanoparticle structure that has a well-defined fragment of a (111) surface, as well as having edges and vertices that can be used to model coordinately unsaturated sites on a particle. In addition, Ag20 has been found to provide a reasonable reference structure for determining the chemical contribution to SERS enhancements.[1] Two different geometries of the Ag20/R6G system are considered in the present study, corresponding to two different binding configurations of R6G to a pristine Ag(111) surface. In addition, we study adsorption of R6G on a flat Ag(111) surface of using plane wave DFT calculations to determine optimized geometries and normal mode properties.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Insights on the Stabilization of Nickel-Rich Cathode Surfaces: Evidence of Inherent Instabilities in the Presence of Conformal Coatings

We report that Ni-rich LiNi 1-x-y MnxCo y O 2 (NMC) cathode materials are being aggressively developed for high-voltage applications such as electric vehicles. These materials are desirable because of their high volumetric energy and power densities. However, degradation phenomena related to surface instabilities of highly charged Ni-rich cathodes have been, and remain, a major concern with respect to cycle life and safety of Li-ion cells. Although many reports exist on the properties and behavior of such materials, sufficient advances have yet to be made with respect to the stabilization of cathode surfaces. Herein, we report on an investigation aimed at probing the inherent stability of electrochemically active Ni δ+ species at the surface of NMC-type, layered-oxide cathode particles. A model system is developed that allows for studies of both surface and bulk species using hard X-ray absorption and electron energy loss spectroscopies. Spectroscopy data collected on cathode electrodes, coated with Al 2 O 3 via atomic layer deposition, reveals that the coating does not enhance the ability to attain, or maintain, fully oxidized Ni (Ni 4+ ) in the near-surface regions of charged cathode particles. The results suggest an inherent instability of Ni δ+ near the surfaces of cathode particles and imply that the strategy of using Al 2 O 3 as a physical barrier coating is not sufficient to overcome these instabilities in layered nickel-rich oxides. Therefore, the system developed for this work can be used as a tool to probe, in working cells, the efficacy of other strategies such as electrolytes, additives, and coatings in stabilizing surface Ni δ+ species in NMC-type cathodes.

36 MATERIALS SCIENCE↗