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At least 235 records · Page 13

Review on organosulfur materials for rechargeable lithium batteries

Organic electrode materials have been considered as promising candidates for the next generation rechargeable battery systems due to their high theoretical capacity, versatility, and environmentally friendly nature. Among them, organosulfur compounds have been receiving more attention in conjunction with the development of lithium-sulfur batteries. Usually, organosulfide electrodes can deliver relatively high theoretical capacity based on reversible breakage and formation of disulfide (S-S) bonds. Here, we provide an overview of organosulfur materials for rechargeable lithium batteries, including their molecular structural design, structure related electrochemical performance study as well as electrochemical performance optimization. In addition, recent progress of advanced characterization techniques for investigation of the structure and lithium storage mechanism of organosulfur electrodes are elaborated. To further understand the perspective application, additive effect of organosulfur compounds for lithium metal anodes, sulfur cathodes as well as high voltage inorganic cathode materials are reviewed with typical examples. Finally, some remaining challenges and perspective of the organosulfur compounds as lithium batteries components are also discussed. This review is intended to serve as a general guidance for researcher to facilitate the development of organosulfur compounds.

25 ENERGY STORAGE↗

Mechanistic Investigation of Redox Processes in Zn-MnO2 battery in Mild Aqueous Electrolytes

Zinc-MnO2 based batteries have acquired attention for grid-level applications, due to impressive theoretical performance, cost effectiveness and intrinsic safety. However, there are still many challenges that remain elusive due to the complex and controversial mechanisms of operation that hinders commercialization. In this work, the detailed redox processes that occur at the cathode during Zn-MnO2 battery operation are elucidated. Using a blend of structural and electrochemical techniques, the redox pairs that occur during operation are mechanistically studied while also showcasing the true impact of the electrolyte additive (0.1 M MnSO4) in a 1 M ZnSO4 electrolyte. An electrochemical quartz-crystal microbalance (EQCM) has been leveraged to reveal the effect of zinc hydroxy sulfate salt (Zn4SO4(OH)6·nH2O) and zinc manganese oxide (ZnxMnyOz) dissolution/deposition, which are believed to be major components during discharge and charge conditions. . These results provide insight not currently available, allowing a holistic view of the electrochemical reaction mechanisms during battery operation.

Rodriguez Perez, Ismael A.↗

Metal–support interactions in metal oxide-supported atomic, cluster, and nanoparticle catalysis

Supported metal catalysts are essential to a plethora of processes in the chemical industry. The overall performance of these catalysts depends strongly on the interaction of adsorbates at the atomic level, which can be manipulated and controlled by the different constituents of the active material (i.e., support and active metal). The description of catalyst activity and the relationship between active constituent and the support, or metal–support interactions (MSI), in heterogeneous (thermo)catalysts is a complex phenomenon with multivariate (dependent and independent) contributions that are difficult to disentangle, both experimentally and theoretically. So-called “strong metal–support interactions” have been reported for several decades and summarized in excellent review articles. However, in recent years, there has been a proliferation of new findings related to atomically dispersed metal sites, metal oxide defects, and, for example, the generation and evolution of MSI under reaction conditions, which has led to the designation of (sub)classifications of MSI deserving to be critically and systematically evaluated. These include dynamic restructuring under alternating redox and reaction conditions, adsorbate-induced MSI, and evidence of strong interactions in oxide-supported metal oxide catalysts. Here, we review recent literature on MSI in oxide-supported metal particles to provide an up-to-date understanding of the underlying physicochemical principles that dominate the observed effects in supported metal atomic, cluster, and nanoparticle catalysts. Critical evaluation of different subclassifications of MSI is provided, along with discussions on the formation mechanisms, theoretical and characterization advances, and tuning strategies to manipulate catalytic reaction performance. We also provide a perspective on the future of the field, and we discuss the analysis of different MSI effects on catalysis quantitatively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure of V-defects in long wavelength GaN-based light emitting diodes

The V-defect is a naturally occurring inverted hexagonal pyramid structure that has been studied in GaN and InGaN growth since the 1990s. Strategic use of V-defects in pre-quantum well superlattices or equivalent preparation layers has enabled record breaking efficiencies for green, yellow, and red InGaN light emitting diodes (LEDs) utilizing lateral injection of holes through the semi-polar sidewalls of the V-defects. In this article, we use advanced characterization techniques such as scattering contrast transmission electron microscopy, high angle annular dark field scanning transmission electron microscopy, x-ray fluorescence maps, and atom probe tomography to study the active region compositions, V-defect formation, and V-defect structure in green and red LEDs grown on (0001) patterned sapphire and (111) Si substrates. We identify two distinct types of V-defects. The “large” V-defects are those that form in the pre-well superlattice and promote hole injection, usually nucleating on mixed (Burgers vector b = ±a±c⁠) character threading dislocations. In addition, “small” V-defects often form in the multi-quantum well region and are believed to be deleterious to high-efficiency LEDs by providing non-radiative pathways. The small V-defects are often associated with basal plane stacking faults or stacking fault boxes. Furthermore, we show through scattering contrast transmission electron microscopy that during V-defect filling, the threading dislocation, which runs up the center of the V-defect, will “bend” onto one of the six {10$\overline{1}$1} semi-polar planes. In conclusion, this result is essential to understanding non-radiative recombination in V-defect engineered LEDs.

42 ENGINEERING↗

A review of the metastable omega phase in beta titanium alloys: the phase transformation mechanisms and its effect on mechanical properties

Since its discovery in 1954, the omega (ω) phase in titanium and its alloys has attracted substantial attention from researchers. The β-to-ω and ω-to-α phase transformations are central to β-titanium alloy design, but the transformation mechanisms have been a subject of debate. With new generations of aberration-corrected transmission electron microscopy and atom probe tomography, both the spatial resolution and compositional sensitivity of phase transformation analysis have been rapidly improving. Furthermore, this review provides a detailed assessment of the new understanding gained and related debates in this field enabled by advanced characterization methods. Specifically, new insights into the possibility of a coupled diffusional-displacive component in the β-to-ω transformation and key nucleation driving forces for the ω-assisted α phase formation are discussed. Additionally, the influence of ω phase on the mechanical properties of β-titanium alloys is also reviewed. Lastly, a perspective on open questions and future direction for research is discussed.

36 MATERIALS SCIENCE↗

Editorial for focus on nanophase materials for next-generation lithium-ion batteries and beyond

Lithium-ion batteries (LIBs) have revolutionized our society in many respects, and we are expecting even more favorable changes in our lifestyles with newer battery technologies. In pursuing such eligible batteries, nanophase materials play some important roles in LIBs and beyond technologies. Here, stimulated by their beneficial effects of nanophase materials, we initiated this Focus. Excitingly, this Focus collects 13 excellent original research and review articles related to the applications of nanophase materials in various rechargeable batteries, ranging from nanostructured electrode materials, nanoscale interface tailoring, novel separators, computational calculations, and advanced characterizations.

25 ENERGY STORAGE↗

Intricate short-range order in GeSn alloys revealed by atomistic simulations with highly accurate and efficient machine-learning potentials

GeSn alloys hold promise for silicon-compatible integrated applications in electronics, photonics, and topological quantum devices. However, understanding their intricate structures using density functional theory (DFT) calculations is hindered by spatiotemporal constraints. To overcome this limitation, we develop highly accurate and efficient machine-learning interatomic potentials based on a neuroevolution potential approach with farthest point sampling on a comprehensive DFT data set. The application of the developed machine-learning potential in large-scale atomistic simulations bridges the spatiotemporal gap between modeling and advanced characterizations, and facilitates the discovery of structural intricacies in GeSn alloys. Through extensive statistical sampling, we identify a type of short-range order (SRO) that is distinguished by both its structural signature and electronic band gap from the SRO structure previously predicted. Modeling based on a large simulation cell reveals the coexistence of nano SRO domains with various degrees of ordering, demonstrating a complex spatial heterogeneity of SRO structure. Finally, our study not only reinforces the significance of fine-level structural information in alloys, but it also constitutes an effective framework for exploring SRO in a broad range of complex alloys based on highly accurate and effective machine-learning potentials.

36 MATERIALS SCIENCE↗

Understanding Environmental Barrier Coating Lifetimes and Performance for Industrial Gas Turbines

Hydrogen or hydrogen blend fuels are expected to replace natural gas in land-based industrial gas turbines (IGTs) to support a greener power economy. Silicon carbide (SiC) base ceramic matrix composites (CMCs) are considered for replacement of Ni-based superalloys to facilitate future efficiency improvements. SiC CMCs require environmental barrier coatings (EBCs) to mitigate volatilization from high-temperature steam, thus making the EBC lifetime critical information for identifying CMC component lifetimes. Here, the goal of this project is to determine the maximum bond coating temperature underneath the EBC for achieving an IGT component lifetime goal of 25,000 h, which is far greater than current CMC component lifetime requirements for aeroturbine applications. To provide data for the lifetime model, laboratory testing used atmospheric plasma-sprayed rare-earth silicate EBCs on monolithic SiC substrates with an intermediate Si bond coating. Specimens exposed to 1-h thermal cycles in flowing air–steam environments and reaction kinetics were assessed from 700 °C to 1350 °C by measuring the thickness of the thermally grown silica scales. The silica growth and phase transformation appear critical in predicting EBC lifetime and several strategies have been explored to reduce the oxide growth rate and improve EBC durability at elevated temperatures. Advanced characterization using Raman spectroscopy has helped clarify this system.

08 HYDROGEN↗

Understanding EBC Lifetimes and Performance for Industrial Gas Turbines

Hydrogen or hydrogen blend fuels are expected to replace natural gas in land-based industrial gas turbines (IGTs) to support a greener power economy. Silicon carbide (SiC) base ceramic matrix composites (CMCs) are considered for replacement of Ni-based superalloys to facilitate future efficiency improvements. SiC CMCs require environmental barrier coatings (EBCs) to mitigate volatilization from high-temperature steam, thus making the EBC lifetime critical information for identifying CMC component lifetimes. The goal of this project is to determine the maximum bond coating temperature underneath the EBC for achieving an IGT component lifetime goal of 25,000 h, which is far greater than current CMC component lifetime requirements for aero-turbine applications. To provide data for the lifetime model, laboratory testing used plasma-sprayed rare-earth silicate EBCs on monolithic SiC substrates with an intermediate Si bond coating. Specimens exposed to 1-h thermal cycles in flowing air-steam environments and reaction kinetics were assessed from 700°-1350°C by measuring the thickness of the thermally grown silica scales. The silica growth and phase transformation appear critical in predicting EBC lifetime and several strategies have been explored to reduce the oxide growth rate and improve EBC durability at elevated temperatures. Advanced characterization using Raman spectroscopy has helped clarify this system.

Ridley, Mackenzie↗

Isoxazole-Based Electrolytes for Lithium Metal Protection and Lithium-Sulfurized Polyacrylonitrile (SPAN) Battery Operating at Low Temperature

A new electrolyte system using isoxazole as the salt dissolving solvent has been developed and studied for lithium metal batteries. By using fluoroethylene carbonate (FEC) as an additive and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) as a diluent for localized high concentration electrolyte (LHCE), isoxazole-based electrolytes were successfully implemented in lithium metal batteries, demonstrating excellent lithium metal protection capability. Utilizing several advanced characterization techniques (including synchrotron-based X-ray absorption spectroscopy and photoelectron spectroscopy), the solid electrolyte interphase (SEI) formed on the Li-metal anode after employing these electrolytes was thoroughly investigated. The high ionic conductivity of isoxazole at low temperature and the low impedance of SEI formed in LHCE significantly improved the low-temperature performance of Li-sulfurized polyacrylonitrile (SPAN) batteries, delivering 273.8 mAh g −1 capacity at −30 °C with 99.85% capacity retention after 50 cycles.

25 ENERGY STORAGE↗

Nanosecond Laser Annealing of NMC 811 Cathodes for Enhanced Performance

Improved performance of lithium-ion batteries (LIBs) plays a critical role in the future of next- generation battery applications. Nickel-rich layered oxides such as LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC 811), are popular cathodes due to their high energy densities. However, they suffer from high surface reactivity, which results in the formation of Li 2 CO 3 passive layer. Herein, we show the role of nanosecond pulsed laser annealing (PLA) in improving the current capacity and cycling stability of LIBs by reducing the carbonate layer, in addition to forming a protective LiF layer and manipulating the NMC 811 microstructures. We use high-power nanosecond laser pulses in a controlled way to create nanostructured surface topography which has a positive impact on the capacity retention and current capacity by providing an increased active surface area, which influences the diffusion kinetics of lithium-ions in the electrode materials during the battery cycling process. Advanced characterizations show that the PLA treatment results in the thinning of the passive Li 2 CO 3 layer, which is formed on as-received NMC811 samples, along with the decomposition of excess polyvinylidene fluoride (PVDF) binder. The high-power laser interacts with the decomposed binder and surface Li + to form LiF phase, which acts as a protective layer to prevent surface reactive sites from initiating parasitic reactions. As a result, the laser treated cathodes show relative increase of the current capacity of up to 50%, which is consistent with electrochemical measurements of LiB cells.

25 ENERGY STORAGE↗

Molten flux growth of single crystals of quasi-1D hexagonal chalcogenide BaTiS3

Abstract BaTiS 3 , a quasi-1D complex chalcogenide, has gathered considerable scientific and technological interest due to its giant optical anisotropy and electronic phase transitions. However, the synthesis of high-quality BaTiS 3 crystals, particularly those featuring crystal sizes of millimeters or larger, remains a challenge. Here, we investigate the growth of BaTiS 3 crystals utilizing a molten salt flux of either potassium iodide, or a mixture of barium chloride and barium iodide. The crystals obtained through this method exhibit a substantial increase in volume compared to those synthesized via the chemical vapor transport method, while preserving their intrinsic optical and electronic properties. Our flux growth method provides a promising route toward the production of high-quality, large-scale single crystals of BaTiS 3 , which will greatly facilitate advanced characterizations of BaTiS 3 and its practical applications that require large crystal dimensions. Additionally, our approach offers an alternative synthetic route for other emerging complex chalcogenides. Graphical Abstract

Materials Science↗

2019 accomplishments: degradation of mechanical properties in structural metals and welds for FTS reservoirs

This report documents work in 2019 at SRNL in support of the Aging and Lifetimes program. Specimens for fracture toughness testing were prepared in prior years by thermally pre-charging samples, provided by Sandia National Laboratories, of welded types 304L and 21-6-9 stainless steels. These samples were pre-charged in 2017. The fracture toughness of the first aged specimens was measured and compared to historical data. The measurements of the 304L and 21-6-9 weld and particularly HAZ represent some of the first fracture data relevant to modern GTS reservoirs. This work represents an on-going collaboration between SRNL and SNL to understand tritium embrittlement of structural metals in Gas Transfer System reservoirs which informs lifetime assessments. Continued testing was conducted on ongoing historical studies, including the effects of very long-term aging, and the relative performance of differently forged stockpile relevant 304L and 316L samples. New samples were pre-charged with tritium and placed in a freezer for an aging study to allow helium to build into the material. The precharged samples consist of smooth and notched tensile samples of 304L stainless steel, as well as tube tensile samples of different thermal treatments supplied by Sandia National Laboratories. Their charging marks the beginning of a new sequence of studies to explore fundamental deformation mechanisms underpinning tritium embrittlement. At predesignated times, samples will be removed from aging and tested to provide data which will help develop an understanding of material degradation with increasing aging time. Also documented is progress in employing various advanced characterization techniques including high resolution electron microscopy, thermally programed desorption, and small angle x-ray scattering, as well as facilities renovations and equipment procurements in support of sustained tritium impacts on materials program at SRNL.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Microstructure, Thermal, and Mechanical Properties Relationships in U and UZr Alloys (Final Report)

Uranium-zirconium (U-Zr) alloys are candidate fuel systems for transmutation based reactors that can be used to burn long-lived minor actinides and fission products in fast spectrum reactors. Metallic fuels have also been gaining more recent attention for applications as accident tolerant fuels, as well as for use in small modular reactors. This research focused on a “science-based” approach to capture the connections between U and U-Zr alloys’ three-dimensional (3-D) microstructure, thermal properties, and mechanical properties through closely coordinated experiments and modeling efforts from the unirradiated to the irradiated fuels. Advanced characterization and modeling techniques were used to understand irradiation-induced microstructural evolution and its direct impact on the thermal and mechanical properties of U and U-Zr fuel. Closely coordinated experiments and modeling were performed to provide crucial data that does not currently exist. Overall, this research spanned multiple length and time scales within the models and experiments. The scope of the research encompassed the understanding of the irradiation effects in U and various U-Zr alloys with particular attention paid to three task areas: (1) microstructural evolution, (2) in-situ/ex-situ thermal and mechanical properties, and (3) multiscale modeling connections to microstructure, thermal, and mechanical properties. This research resulted in (1) the 3-D characterization of neutron irradiated U-Zr fuel in multiple phase regions to better understand fission gas swelling and constituent redistribution, (2) development of a microstructural model linking thermal and mechanical properties via in situ Raman and nanoindentation, (3) and mesoscale phase field modeling was coupled with the AEH method in the MOOSE framework was used to calculate the effective thermal conductivities of U-Zr fuels consisting of α-U and δ-UZr 2 heterogeneous microstructures.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Growth of New High-Quality and Large-Size Single Crystals via High Pressure Floating-Zone Technique

This award supports experimental materials physics research on a class of technologically relevant materials that cannot form under ambient conditions. With the complementary expertise at Louisiana State University (LSU) and infrastructure at Oak Ridge National Laboratory (ORNL), single crystals of these materials will be synthesized using the high-pressure floating-zone technique. Our ability to grow high-quality single crystals will facilitate advanced characterization of these materials and improve the scientific outcomes. In addition to in-house material characterization, the principle investigator will partner with scientists at ORNL and Brookhaven National Laboratory (BNL) to tackle materials problems using the state-of-the-art characterization techniques. This will allow us to explore the fundamental physics underlying the emergent phenomena only seen in materials prepared under extreme conditions. Our ultimate goal is to address one of the grand challenges of materials science: how do complex phenomena emerge from simple ingredients? The proposed project will also spearhead a unique opportunity to train “new breed” scientists, co-advised by experts at both LSU and U. S. Department of Energy National Laboratories. They will be essential for expanding materials physics research with ability to grow crystals, characterize their properties, and design new materials -- an imperative skill that is scarce in the U. S. scientific community.

36 MATERIALS SCIENCE↗

Center for Gas Separations (CGS)

The total energy consumption in the U.S. has been rising steadily for decades, and it currently amounts to ~98,000 TBtu/yr, with approximately 30% of this total attributable to the industrial sector. Reasonable estimates indicate that 45–55% of total industry energy consumption derives from chemical separations, and for example, over 120 TBtu/yr alone is used in carrying out olefin/paraffin separations via energy-intensive cryogenic distillation. Therefore, the pursuit of new, even radically different approaches to some of the most energy-intensive industrial separations processes is an imperative scientific pursuit for reducing energy consumption toward a more sustainable future. Adsorbent and membrane-based separations can require a fraction of the energy needed for distillation methods, and as such are considered promising solutions for balancing increasing energy demand in the U.S. with the need for a massive reduction in energy consumption. Although considerable research effort has been devoted to the design of materials capable of carrying out various gas separations, usually operating through size-selective, chemisorptive, or physisorptive mechanisms, it remains a great challenge to design materials that function adequately for real-world applications. Indeed, the chemical and physical differences between molecules in gas mixtures of interest are often small, and therefore it is necessary, through the use of nanoscience and synthetic chemistry, to engineer unprecedented molecular-level control in adsorbate–adsorbent interactions. The overarching mission of the Center for Gas Separations (CGS) was to discover fundamental innovations that have the potential to dramatically reduce the energy associated with critical gas separations. In particular, the CGS developed novel synthetic routes, guided by molecular chemistry principles, as well as advanced characterization and computational methods, that have enabled the discovery of new materials and membranes tailor-made to exhibit exceptional performance for a range of gas separations processes, as required in the clean use of fossil fuels and in reducing CO 2 emissions from industry. A challenge of this magnitude required the collaboration and synergy of a large team of researchers with expertise in materials synthesis, characterization, and computations. During the 11-year project period, the CGS created a range of new materials within the family of highly-tunable, porous solids known as metal–organic frameworks (MOFs). These new frameworks demonstrate novel mechanisms for key industrial gas separations, including revolutionary new cooperative adsorption processes that enable low-energy CO 2 and CO capture, and are capable of efficiently separating olefins from paraffins, O 2 from air, and the shape-selective separation of alkane isomers. In addition, the CGS developed new strategies for incorporating these materials into composite membranes toward highly efficient and selective membrane-based separations. As a testament to the success of the CGS, two start-up companies, Mosaic Materials,4 Inc. and Flux Technology, Inc., grew out of these research efforts, and these companies are seeking to commercialize MOF and composite membranes materials for key separations in industry, including large-scale CO 2 capture and hydrocarbon separations, respectively. Another company, framergy, Inc., licensed IP resulting from CGS research toward the commercialization of adsorbents for various energy-relevant applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Battery500 Consortium: Development of High Capacity Cathodes and Robust Solid Electrolytes

As the world have witnessed the tremendous development in portable electronic devices as well as electric vehicles, the current generation lithium-ion battery is unlikely to satisfy the bourgeon of market and the demand of the customers. A next generation battery, with cell energy density higher than 500 Wh kg -1 , needs to be developed to meet the growth of the industry. With its high theoretical capacity (3,860 mAh g -1 , or 2,061 mAh cm -3 ) and low electrochemical potential (–3.04 V versus the standard hydrogen electrode), lithium metal has been regarded as the ideal candidate for the next generation battery anode. In fact, Lithium metal anode is irreplaceable for Lithium-Sulfur chemistry. However, the continuous formation of inactive Li, which eventually leads the loss of reversible capacity of the cell, has prevented lithium metal to be used as anode in commercial rechargeable cells. The ultimate goal of the project is to propose a pathway to enable Li metal battery for stable cycling at 99.9% of Coulombic efficiency with energy density higher than 500 Wh kg -1 . A variety of advanced characterization tools, electrolyte systems, 3D current collectors and failure analysis methodologies have been developed throughout the project during the past 5 years. The UCSD effort is carried out by the groups of Ping Liu and Shirley Meng.

25 ENERGY STORAGE↗

Enabling New Approaches to Low-Cost Dopant Patterning for Interdigitated Back Contact Crystalline Silicon Solar Cells: Cooperative Research and Development, CRADA Number CRD-17-00665 (Final Report)

NREL is sub to the Department of Energy (DOE) Photovoltaic Research & Development (PVRD) project, titled "New Approaches to Low-Cost Scalable Doping for Interdigitated Back Contact Crystalline Silicon Solar Cells", awarded to Colorado School of Mines. The goal of this project was to develop an industrially relevant dopant patterning technique that enable high performing, cost efficient Interdigitated Back Contact (IBC) solar cells based on n-Cz silicon wafer. Several possibilities were explored at the beginning of the project and the masked plasma deposition was deselected as the most promising and industrially relevant. This method was thoroughly explored ion the course of the project, its limitations revealed and mitigated. NREL successfully the masked deposition integrated into the cell's process flow and produced the cells, alongside with numerous process development steps and application of in-house advanced characterization techniques. The report describes these developments by the task and in detail.

14 SOLAR ENERGY↗