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At least 55 records · Page 3

Development of Next Generation Hierarchical Hybrid Cu-Si anode Batteries via Direct-Ink Writing Application: End of (6th) Month Report - November 2025

Sustainable renewable energy continues to be in dire need to effectively combat global warming. Emerging technology for electric vehicles/ devices remains in high demand that is not only lower in cost, more efficient, but safer in comparison to commercial materials on the market. Although first-generation lithium-ion batteries have exhibited extensive commercial application, conventional graphite no longer meets this increasing demand as an efficient anode material. Due to the fact that graphite has a subpar theoretical specific capacity (372 mAh g -1 ), thus significant limitations in rate capability (for potential faster charging at higher C-rates currently commercially available.). Alternatively, silicon has gained significant attention as a superior candidate to potentially surpass graphite. Due to silicon’s exceedingly high theoretical capacity (4,200 mAh g -1 ) in comparison to standard graphite, its abundance thus in turn it’s low-cost, in addition to exhibiting a significantly low working potential (< 0.4 V vs Li/Li + ). However, one of the main (and most detrimental) challenges is silicon’s tendency to expand in volume (> 300%) upon discharge as it begins the lithiation process. As a direct result, it causes not only for the particles to both crack and pulverize under mechanical stress as the volume continues to expand and contract during cycling. Upon assembling the cell, it needs to undergo ‘charging’ for initially discharging/ ‘activating’ the cell, otherwise commonly known as the ‘formation’ step. As a result a solid electrolyte interface (SEI) layer begins to form at the anode surface because some of the electrolyte begins to react during the formation process. However, this (SEI) layer is deemed as a ‘protective’ interlayer because in theory it prevents further reaction as the cell continues to cycle. However, due to the volume change it causes significant degradation at the interface. As cracking starts to occur at the anode surface, it results in a ‘new’ altered surface with each cycle that causes further reaction with the electrolyte as a byproduct quickly consuming active Li/ and more electrolyte. Thus, fracturing this ‘protective layer,’ causing significantly higher impedance as a result, and in turn a decline in capacity due to active Li-loss. In addition to the active material exfoliating off from the current collector, further contributing to the steady decline in capacity and overall performance. Current state of the art Si-anode batteries on the market range between a maximum content of 5-10 Si wt%. It has been previously reported Tesla has utilized SiO x -C anodes containing 5 wt% Si within their ‘Model 3/ Model X’ electric vehicles. However, more recent ‘Model 3’ vehicles have started to incorporate 10 Si wt%, in which they were able to increase their energy density upwards by approximately 30%. Recent effort has been focused on continuing to increase the wt% of Si being utilized, eventually to 100 wt% of Si, to maximize the energy density even further.

36 MATERIALS SCIENCE

Simplified Abrasion Test Methodology for Candidate EVA Glove Lay-Ups

During the Apollo Program, space suit outer‐layer fabrics were badly abraded after performing just a few extravehicular activities (EVAs). For example, the Apollo 12 commander reported abrasive wear on the boots that penetrated the outer‐layer fabric into the thermal protection layers after less than 8 hrs of surface operations. Current plans for the exploration planetary space suits require the space suits to support hundreds of hours of EVA on a lunar or Martian surface, creating a challenge for space suit designers to utilize materials advances made over the last 40 years and improve on the space suit fabrics used in the Apollo Program. Over the past 25 years the NASA Johnson Space Center Crew and Thermal Systems Division has focused on tumble testing as means of simulating wear on the outer layer of the space suit fabric. Most recently, in 2009, testing was performed on 4 different candidate outer layers to gather baseline data for future use in design of planetary space suit outer layers. In support of the High Performance EVA Glove Element of the Next Generation Life Support Project, testing a new configuration was recently attempted in which require 10% of the fabric per replicate of that need in 2009. The smaller fabric samples allowed for reduced per sample cost and flexibility to test small samples from manufacturers without the overhead to have a production run completed. Data collected from this iteration was compared to that taken in 2009 to validate the new test method. In addition the method also evaluated the fabrics and fabric layups used in a prototype thermal micrometeoroid garment (TMG) developed for EVA gloves under the NASA High Performance EVA Glove Project. This paper provides a review of previous abrasion studies on space suit fabrics, details methodologies used for abrasion testing in this particular study, results of the validation study, and results of the TMG testing.

Rabel, Emily

Photovoltaic-Panel Laminator

Two-piece unit heats and presses protective layers to form laminate. Rubber diaphragm between upper and lower vacuum chambers alternates between neutral position and one that presses against solar-cell array, supplying distributed force necessary to press layers of laminate together. Encapsulation helps to protect cells from environment and to ensure long panel life while allowing efficient generation of electricity from Sunlight.

Keenan, R.

Enhanced Far Ultra-Violet Optical Properties of Physical Vapor Deposited Aluminum Mirrors Through Fluorination

Astronomical instrumentation for measurements in the Far Ultra-Violet (FUV, 90-200 nm) typically use aluminum (Al) thin films due to their high reflectance over this wavelength range. However, the native aluminum oxide layer that forms on Al upon exposure to the atmosphere is strongly absorbing in this wavelength range, requiring that the films be protected with a dielectric that inhibits oxidation. Typically, magnesium fluoride (MgF 2 ) or lithium fluoride (LiF) coatings are used as protective layers, but each has shortcomings. For example, MgF 2 has an absorption cutoff at 115 nm reducing performance in a critical part of the FUV spectrum of observational interest. A viable option to access these lower wavelengths could be the use of the LiF overcoat as it has a lower absorption cutoff at 102.5 nm, but it is hygroscopic and thus susceptible to degradation in humid conditions. An approach to reduce the hygroscopic nature of LiF would be to implement a passivation process during the deposition of both Al+LiF coatings. Our team at GSFC has developed a new reactive Physical Vapor Deposition (rPVD) process that consists of a fluorination process with XeF 2 gas combined with our traditional PVD process. We have found that this new rPVD coating process offers a protected version of Al+LiF with a more environmentally stable and more transparent LiF layer, along with unprecedent reflectivity. The process starts with a bare optically smooth substrate that is coated with Al in an ultra-high vacuum (UHV) chamber by the conventional PVD process. Then, the bare Al mirror is immediately exposed to a reactive XeF 2 gas before and after the application of the flash PVD evaporated LiF layer. We have also been investigating the use of this rPVD coating process for potential efficiency enhancements of Si-based gratings. Since it is known that the XeF 2 vapor is a strong Si etchant, we are investigating if the native SiO 2 layer on Si is sufficient to protect the groove profile of e-beam-ruled Si gratings from degradation. We will report on the characterization of various Al+LiF witness mirror coatings (both on borosilicate and Si) performed under various deposition conditions using the XeF 2 passivation process. These tests include XPS to determine film stoichiometry and AFM/SEM to measure surface roughness and any etching on the Si substrate. We will also report on FUV reflectance and spectroscopic ellipsometry to characterize optical constants of these passivated films in the UV/Visible/NIR spectral ranges.

Engineering (General)

Enhanced Far Ultra-Violet Optical Properties of Physical Vapor Deposited Aluminum Mirrors Through Fluorination

Astronomical instrumentation for measurements in the Far Ultra-Violet (FUV, 90-200 nm) typically use aluminum (Al) thin films due to their high reflectance over this wavelength range. However, the native aluminum oxide layer that forms on Al upon exposure to the atmosphere is strongly absorbing in this wavelength range, requiring that the films be protected with a dielectric that inhibits oxidation. Typically, magnesium fluoride (MgF 2 ) or lithium fluoride (LiF) coatings are used as protective layers, but each has shortcomings. For example, MgF 2 has an absorption cutoff at 115 nm reducing performance in a critical part of the FUV spectrum of observational interest. A viable option to access these lower wavelengths could be the use of the LiF overcoat as it has a lower absorption cutoff at 102.5 nm, but it is hygroscopic and thus susceptible to degradation in humid conditions. An approach to reduce the hygroscopic nature of LiF would be to implement a passivation process during the deposition of both Al+LiF coatings. Our team at GSFC has developed a new reactive Physical Vapor Deposition (rPVD) process that consists of a fluorination process with XeF 2 gas combined with our traditional PVD process. We have found that this new rPVD coating process offers a protected version of Al+LiF with a more environmentally stable and more transparent LiF layer, along with unprecedent reflectivity. The process starts with a bare optically smooth substrate that is coated with Al in an ultra-high vacuum (UHV) chamber by the conventional PVD process. Then, the bare Al mirror is immediately exposed to a reactive XeF 2 gas before and after the application of the flash PVD evaporated LiF layer. We have also been investigating the use of this rPVD coating process for potential efficiency enhancements of Si-based gratings. Since it is known that the XeF 2 vapor is a strong Si etchant, we are investigating if the native SiO 2 layer on Si is sufficient to protect the groove profile of e-beam-ruled Si gratings from degradation. We will report on the characterization of various Al+LiF witness mirror coatings (both on borosilicate and Si) performed under various deposition conditions using the XeF 2 passivation process. These tests include XPS to determine film stoichiometry and AFM/SEM to measure surface roughness and any etching on the Si substrate. We will also report on FUV reflectance and spectroscopic ellipsometry to characterize optical constants of these passivated films in the UV/Visible/NIR spectral ranges.

Engineering (General)

Enhanced Far Ultra-Violet Optical Properties of Physical Vapor Deposited Aluminum Mirrors Through Fluorination

Astronomical instrumentation for measurements in the Far Ultra-Violet (FUV, 90-200 nm) typically use aluminum (Al) thin films due to their high reflectance over this wavelength range. However, the native aluminum oxide layer that forms on Al upon exposure to the atmosphere is strongly absorbing in this wavelength range, requiring that the films be protected with a dielectric that inhibits oxidation. Typically, magnesium fluoride (MgF 2 ) or lithium fluoride (LiF) coatings are used as protective layers, but each has shortcomings. For example, MgF 2 has an absorption cutoff at 115 nm reducing performance in a critical part of the FUV spectrum of observational interest. A viable option to access these lower wavelengths could be the use of the LiF overcoat as it has a lower absorption cutoff at 102.5 nm, but it is hygroscopic and thus susceptible to degradation in humid conditions. An approach to reduce the hygroscopic nature of LiF would be to implement a passivation process during the deposition of both Al+LiF coatings. Our team at GSFC has developed a new reactive Physical Vapor Deposition (rPVD) process that consists of a fluorination process with XeF 2 gas combined with our traditional PVD process. We have found that this new rPVD coating process offers a protected version of Al+LiF with a more environmentally stable and more transparent LiF layer, along with unprecedent reflectivity. The process starts with a bare optically smooth substrate that is coated with Al in an ultra-high vacuum (UHV) chamber by the conventional PVD process. Then, the bare Al mirror is immediately exposed to a reactive XeF 2 gas before and after the application of the flash PVD evaporated LiF layer. We have also been investigating the use of this rPVD coating process for potential efficiency enhancements of Si-based gratings. Since it is known that the XeF 2 vapor is a strong Si etchant, we are investigating if the native SiO 2 layer on Si is sufficient to protect the groove profile of e-beam-ruled Si gratings from degradation. We will report on the characterization of various Al+LiF witness mirror coatings (both on borosilicate and Si) performed under various deposition conditions using the XeF 2 passivation process. These tests include XPS to determine film stoichiometry and AFM/SEM to measure surface roughness and any etching on the Si substrate. We will also report on FUV reflectance and spectroscopic ellipsometry to characterize optical constants of these passivated films in the UV/Visible/NIR spectral ranges.

Engineering (General)

Kinetics and mechanism of corrosion of SiC by molten salts

Corrosion of sintered alpha-SiC under thin films of Na2CO3/CO2, Na2SO4/O2, and Na2SO4/SO3 was investigated at 1000 C. Chemical analysis was used to follow silicate and silica evolution as a function of time. This information coupled with morphology observations leads to a detailed corrosion mechanism. In all cases the corrosion reactions occur primarily in the first few hours. In the Na2CO3/CO2 case, rapid oxidation and dissolution lead to a thick layer of silicate melt in about 0.25 h. After this, silica forms a protective layer on the carbide. In the Na2SO4/O2 case, a similar mechanism occurs. In the Na2SO4/SO3 case, a porous nonprotective layer of SiO2 grows directly on the carbide, and a silicate melt forms above this. In addition, SiO2 and regenerated Na2SO4 form at the melt/gas interface due to reaction of silicate with SO3 and SO2 + O2. The reaction slows when the lower silica layer becomes nonporous.

Jacobson, N. S.

Vapor grown silicon dioxide improves transistor base-collector junctions

Vapor grown silicon dioxide layer protects base-collector junction in silicon planar transistors during the emitter diffusion process. This oxide fills in any imperfections that exist in the thermally grown oxide layer and is of greater thickness than that layer. This process is used to deposit protective silicon dioxide coatings on optical surfaces.

Carley, D. R.

Monitoring of Observation Errors in the Assimilation of Satellite Ozone Data

The stratospheric ozone layer protects life on Earth from the harmful effects of solar ultravioiet radiation. The ozone layer is currently in a fragile state because of depletion caused by man-made chemicals, especially chlorofluorocarbons. The state of the ozone layer is being monitored and evaluated by scientific experts around the world, in order to help policy makers assess the impacts of international protocols that control the production and release of ozone depleting chemicals. Scientists use a variety ozone measurements and models in order to form a comprehensive picture about the current state of the ozone layer, and to predict the future behavior (expected to be a recovery, as the abundance of the depleting chemicals decreases). Among the data sets used, those from satellite-borne instruments have the advantage of providing a wealth of information about the ozone distribution over most of the globe. Several instruments onboard American and international satellites make measurements of the properties of the atmosphere, from which atmospheric ozone amounts are estimated; long-term measurement programs enable monitoring of trends in ozone. However, the characteristics of satellite instruments change in time. For example, the instrument lenses through which measurements are made may deteriorate over time, or the satellite orbit may drift so that measurements over each location are made later and later in the day. These changes may increase the errors in the retrieved ozone amounts, and degrade the quality of estimated ozone amounts and of their variability. Our work focuses on combining the satellite ozone data with global models that capture atmospheric motion and ozone chemistry, using advanced statistical techniques: this is known as data assimilation. Our method provides a three-dimensional global ozone distribution that is consistent with both the satellite measurements and with our understanding of processes (described in the models) that control ozone distribution. Through the monitoring of statistical properties of the agreement between the data and the model, this approach also enables us to detect changes in the quality of ozone data retrieved from satellite-borne instrument measurements. This paper demonstrates that calculations of the changes in satellite data quality, and the impact these changes on the estimates of the global ozone distribution, can assist in maintaining the uniform quality of the satellite ozone data throughout the lifetime of these instruments, thus contributing to our understanding of long-term ozone change.

Stajner, Ivanka

Stoichiometric effects on grain growth in zirconium carbide coatings for high-temperature nuclear fuel

Interest in coated particle fuel for space nuclear propulsion (SNP) has expanded in recent years due to successful demonstrations of the resiliency of the coatings to extreme environments. For SNP applications, the coating layer for the particle design needs to be able to withstand exposure to high temperature hydrogen during operating conditions. ZrC has been proposed as a protective layer, however, it is important to understand the high temperature behavior to ensure adequate protection to this fuel. In this study, surrogate ZrC coated particles were heat treated at 1900 °C up to 300 min, to examine how the microstructure evolves when exposed to high temperature. Scanning electron microscopy and electron backscatter diffraction (EBSD) were conducted to determine grain size and grain boundary character and orientation to determine the degree of change in the ZrC layer post heat treatment. Raman spectroscopy provided insight to understand how the as-fabricated stoichiometry of each sample contributed to the differences in grain growth behavior. Despite the as-fabricated samples showing a similar initial grain size and grain boundary character, the samples with a higher amount of excess carbon exhibited smaller grain areas and slower growth rates when exposed to 1900 °C. In conclusion, this investigation details the as-fabricated microstructure of the ZrC layer, specifically grain size, evolved under high temperature as this can impact the performance of the fuel under operating conditions.

EBSD

Mitigating Transition Metal Dissolution from Mn-rich Cathodes: Influence of Processing and Testing Methods

Manganese-rich oxides continue to gain interest with respect to the development of Earth-abundant options for lithium-ion cathodes. Of the unique challenges that hinder the respective performance of various classes of such materials, manganese dissolution still stands as a common theme. The work herein explores Li 3 PO 4 as a robust surface protection layer on a prototypical, Co-free, manganese-rich cathode in the way of a lithium- and manganese-rich oxide. The study highlights the critical importance of synthesis and processing in realizing optimal performance of a given surface treatment by comparing sol-gel and atomic layer deposition methods. Furthermore, cycling protocols are emphasized as a critical factor in adequately gauging the efficacy of surface protection strategies to mitigate manganese dissolution and the subsequent electrochemical consequence. Optimized Li 3 PO 4 coatings coatings on lithium- and manganese-rich cathode particles are shown to greatly mitigate capacity fade, impedance rise, pore/void formation and mechanical damage during long-term cycling.

Mallick, Subhadip [Argonne National Laboratory (AN

In-situ hydrogen microstructural characterization of Si heterojunction passivation: Addressing V OC degradation and mitigation pathways

Si heterojunction (SHJ) solar cells have demonstrated record efficiency >27%, approaching the theoretical limit of ≈ 29%, primarily due to best surface/interface defect passivation provided by deposited thin layers of hydrogenated amorphous silicon (a-Si:H). Such excellent surface/interface passivation reduces recombination loss and result in >100 mV improvement of cell open circuit voltage (V OC ) to ≈ 750 mV, thus the cell efficiency. However, fielded SHJ modules exhibit loss of V OC and hence efficiency over time in years, presumably due to degradation related to a-Si:H layers. This adversely affects the technology’s market acceptance, and levelized cost of energy (LCOE). It is hypothesized that the origin of a-Si:H degradation is somehow related to the presence of weak Si–Si bonds and hydrogen in a-Si:H films. The objective of this project is to test this hypothesis by directly measuring chemical and structural changes occurring within SHJ component layers and solar cells. This is achieved by developing an innovative in-situ Fourier transform infrared (FTIR) spectrometry apparatus to monitor hydrogen microstructural changes occurring within amorphous silicon and decipher hydrogen evolution kinetics over time when samples are exposed to heat and/or light stress. These in-situ measured hydrogen microstructural changes are correlated to the changes in effective minority carrier lifetime (τ eff ), implied V OC (iV OC ), surface recombination velocity (S), and cell V OC . These mechanistic understandings will provide critical guidance to mitigate the V OC -driven degradation of SHJ solar cell performance. Passivation optimization and degradation analysis of individual SHJ component structures were achieved through systematic deposition of three symmetric structures and the completed SHJ solar cell structure. The three symmetric structures used were intrinsic a-Si:H [(i)a-Si:H] layers in a bilayer structure, intrinsic and p-type doped stacked layers [(i-p)a-Si:H] representing the front heterojunction in the SHJ cell, and intrinsic and n-typed doped stacked layers [(i-n)a-Si:H] representing the back-side back surface field (BSF) in the SHJ cell. State-of-the-art passivation qualities are demonstrated by a champion iV OC of 740 mV for the (i)a-Si:H layers, and the (i-n)a-Si:H symmetric structure. A 725 mV iV OC is observed for the (i-p)a-Si:H symmetric structure. These symmetric passivated SHJ component structures were subsequently subjected to different accelerated lifetime (ALT) stressors to identify which conditions contribute the most to iV OC degradation. Degradation of the thin (10 nm) (i)a-Si:H passivation layers without any additional overlying layers is minimal; complexity of this study arises due to unavoidable surface oxidation of (i)a-Si:H layer during most of the stress application, which is likely irrelevant for a full SHJ cell configuration with overlying protective layers. The iV OC degradation of symmetric structures is found to occur primarily at the (i-p)a-Si:H passivation stack under dark heat stress with associated hydrogen loss from the (p)a-Si:H layer. An activation energy for increase in S (defect creation) of 0.65 eV can be correlated to the activation energy of ≈ 0.4 eV for hydrogen loss from the (i-p)a-Si:H stack. This also suggests the presence of weakly bonded hydrogen in the (p)a-Si:H films, which effuses out of the film stack at such low activation energy. When light and heat stress are applied together, similar hydrogen loss from (i-p)a-Si:H stack is observed, however, does not appreciably degrade iV OC or increase S. This is an important result and departure from direct correlation between hydrogen loss and defect creation. This perhaps indicates additional defect chemistries or annealing that might be occurring in the presence of light requiring further detailed defect measurements. The full SHJ cell structure used for this project is depicted in Fig.1(d). SHJ cells with an initial V OC ≈ 700 mV were fabricated and subjected to similar ALT stress conditions. Cell V OC is found to degrade the most under dark heat stress and is confirmed by observed hydrogen migration out of the (i-p)a-Si:H stack. However, hydrogen cannot escape from the cell stack, it accumulates near the (p)a-Si:H/ITO contact interface, where ITO acts as a barrier preventing hydrogen loss. Furthermore, light-heat combined stress does not degrade V OC appreciably, confirming the occurrence of a defect annealing process.

14 SOLAR ENERGY

Real-time thickness measurement of MCC ablator material

One of the most favorable characteristics of the Space Shuttle Program is the reusability of two of its primary components: the orbiter itself and the Solid Rocket Boosters (SRB). The SRB's provide the primary source of propulsion for the Space Shuttle during take-off after which they are recovered for refurbishment and reuse. During refurbishment, the SRB's are stripped of all remaining ablative (heat resistant) coating. A new layer is applied to the appropriate sections (nose cone, frustum, forward skirt, and aft skirt). It is the process of applying the ablative coating which provided the impetus for this project. The thickness of this protective layer is considered to be of primary importance to the level of thermal protection provided. The objectives of this effort are to investigate possible techniques for measuring the thickness of MCC, and if possible to test the specific capabilities of those considered good candidates for implementation. The system would be able to take measurements in real-time as close to the spray gun as possible. This will allow the information to be used in the control of the process without an inordinate time delay between a measurement and its appropriate response. The thickness of the deposited material is to be measured with less than 0.100 in if uncertainty. This is the defined tolerance window for the ablator thickness. Finally, it must operate within the confines of the chamber which encloses the turntable, robot, and spray system, and therefore is required to be insensitive to, or at least maintainable in, that environment.

Greenway, R. Bryan, Jr.

Coating permits use of strain gage in water and liquid hydrogen

Strain gage installation covered with a three-layer coating of commercial materials makes measurements in water and liquid hydrogen. It consists of a selected foil strain gage bonded with a modified commercial heat-curring epoxy cement. The outer protective layer of the gage installation may develop cracks when immersed in liquid hydrogen.

Berven, B. B.

Mass Efficiencies for Common Large-Scale Precision Space Structures

This paper presents a mass-based trade study for large-scale deployable triangular trusses, where the longerons can be monocoque tubes, isogrid tubes, or coilable longeron trusses. Such structures are typically used to support heavy reflectors, solar panels, or other instruments, and are subject to thermal gradients that can vary a great deal based on orbital altitude, location in orbit, and self-shadowing. While multi layer insulation (MLI) blankets are commonly used to minimize the magnitude of these thermal disturbances, they subject the truss to a nonstructural mass penalty. This paper investigates the impact of these add-on thermal protection layers on selecting the lightest precision structure for a given loading scenario.

triangular truss

Photoelectrochemical Proton-Coupled Electron Transfer of TiO 2 Thin Films on Silicon

TiO 2 thin films are often used as protective layers on semiconductors for applications in photovoltaics, molecule–semiconductor hybrid photoelectrodes, and more. Experiments reported here show that TiO 2 thin films on silicon are electrochemically and photoelectrochemically reduced in buffered acetonitrile at potentials relevant to photoelectrocatalysis of CO 2 reduction, N 2 reduction, and H 2 evolution. On both n-type Si and irradiated p-type Si, TiO 2 reduction is proton-coupled with a 1e – :1H + stoichiometry, as demonstrated by the Nernstian dependence of the Ti 4+/3+ E 1/2 on the buffer pK a . Experiments were conducted with and without illumination, and a photovoltage of ∼0.6 V was observed across 20 orders of magnitude in proton activity. The 4 nm films are almost stoichiometrically reduced under mild conditions. The reduced films catalytically transfer protons and electrons to hydrogen atom acceptors, based on cyclic voltammogram, bulk electrolysis, and other mechanistic evidence. TiO 2 /Si thus has the potential to photoelectrochemically generate high-energy H atom carriers. Characterization of the TiO 2 films after reduction reveals restructuring with the formation of islands, rendering TiO 2 films as a potentially poor choice as protecting films or catalyst supports under reducing and protic conditions. Altogether, this work demonstrates that atomic layer deposition TiO 2 films on silicon photoelectrodes undergo both chemical and morphological changes upon application of potentials only modestly negative of RHE in these media. While the results should serve as a cautionary tale for researchers aiming to immobilize molecular monolayers on “protective” metal oxides, the robust proton-coupled electron transfer reactivity of the films introduces opportunities for the photoelectrochemical generation of reactive charge-carrying mediators.

Electrodes

Modulating Surface Anionic Redox Chemistry toward Highly Stable Li-Rich Cathodes with Negligible Oxygen Loss

Low initial Coulombic efficiency and severe capacity/voltage fading during cycling caused by serious irreversible oxygen release, especially in the initial cycle, and resultantly induced unstable electrode/electrolyte interfacial chemistry, largely prohibit the commercial application of high-capacity Li-rich layered oxide cathodes (LLOs). Here, in this work, a dual reductive gas interface cotreatment strategy is applied to regulate the lattice oxygen redox activity and reversibility with a multiple defective structure design including Li/O/TM (TM = transition metal) vacancies and the intrinsic TM doping as well as a full-surface protective layer, which can suppress the irreversible TM migration and then undesirable phase transformation, resisting the corrosion of electrolyte during cycling effectively. Importantly, the introduced reversible SO 3 2- /SO 4 2- redox couple that provides extra capacity compensation could alleviate the distortion of oxygen-central octahedral structure and structural collapse caused by immoderate oxygen oxidation. Thus, the lattice oxygen redox chemistry is optimized, with negligible oxygen loss during the initial cycle. And the designed AS-LLO cathode with greatly enhanced structure stability shows high-capacity retentions of 99.2% at 0.3C after 100 cycles and 82.4% even after 1000 cycles at 5C. This work provides a guideline for manipulating the oxygen redox chemistry to achieve long-lifespan Li-rich layered oxide cathodes for high-energy-density lithium batteries.

25 ENERGY STORAGE

Progress in Fabrication of Rocket Combustion Chambers by VPS

Several documents in a collection describe aspects of the development of advanced materials and fabrication processes intended to enable the manufacture of advanced rocket combustion chambers and nozzles at relatively low cost. One concept discussed in most of the documents is the fabrication of combustion-chamber liners by vacuum plasma spraying (VPS) of an alloy of 88Cu/8Cr/4Nb (numbers indicate atomic percentages) -- a concept that was reported in "Improved Alloy for Fabrication of Combustion Chambers by VPS" (MFS-26546). Another concept is the deposition of graded-composition wall and liner structures by VPS in order to make liners integral parts of wall structures and to make oxidation- and thermal-protection layers integral parts of liners: The VPS process is started at 100 percent of a first alloy, then the proportion of a second alloy is increased gradually from zero as deposition continues, ending at 100 percent of the second alloy. Yet another concept discussed in one of the documents is the VPS of oxidation-protection coats in the forms of nickel-and-chromium-containing refractory alloys on VPS-deposited 88Cu/8Cr/4Nb liners.

Holmes, Richard R.