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At least 73 records · Page 4

Lithiophilic CoF 2 @C hollow spheres towards spatial lithium deposition for stable lithium metal batteries

Lithium metal (LM) is a promising anode for next-generation batteries due to its high theoretical capacity and low electrode potential. Nonetheless, side reactions, volume change, and unwanted lithium dendrite growth seriously limit the practical application of LM. Herein, with the aid of a hard template approach, a novel lithiophilic CoF 2 -carbon hollow sphere (CoF 2 @C-HS) composite material is successfully prepared via a facile in-situ fluorination and etching strategy. The lithiophilic CoF 2 acts as nucleation sites to reduce nucleation overpotential as well as induces the spatial Li deposition and the formation of LiF-rich solid electrolyte interphase (SEI), and the hollow carbon matrix can enhance the electrical conductivity and offer free space for LM deposition. Theoretical simulations reveal that the synergistic effect of lithiophilic CoF 2 and hollow carbon matrix homogenizes the electric field distribution and Li + flux. Benefiting from these advantages, the CoF 2 @C-HS-modified copper substrate electrode delivers an enhanced Coulombic efficiency (CE) of 93.7% for 280 cycles at 1 mA cm –2 and 1 mA h cm –2 . The symmetrical cell using CoF 2 @C-HS can stably cycle more than 1800 h with a low voltage hysteresis of 11 mV at a current density of 0.5 mA cm –2 and an areal capacity of 0.5 mA h cm –2 . Moreover, the Li@CoF 2 @C-HS composite anode enables more than 300 stable cycles at 1 C with a capacity retention of 95% in LiFePO 4 -based full cell and 110 stable cycles at 1 C in LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811)-based high-voltage full cell. Finally, this work might shed a new light on designing lithiophilic hosts to spatially confine LM deposition, realizing dendrite-free LM anodes and the practical applications of LM batteries.

25 ENERGY STORAGE↗

Deconstructing proton transport through atomically thin monolayer CVD graphene membranes

Selective proton (H + ) permeation through the atomically thin lattice of graphene and other 2D materials offers new opportunities for energy conversion/storage and novel separations. Practical applications necessitate scalable synthesis via approaches such as chemical vapor deposition (CVD) that inevitably introduce sub-nanometer defects, grain boundaries and wrinkles, and understanding their influence on H + transport and selectivity for large-area membranes is imperative but remains elusive. Using electrically driven transport of H + and potassium ions (K + ) we probe the influence of intrinsic sub-nanometer defects in monolayer CVD graphene across length-scales for the first time. At the micron scale, the areal H + conductance of CVD graphene (~4.5-6 mS cm -2 ) is comparable to that of mechanically exfoliated graphene indicating similarly high crystalline quality within a domain, albeit with K + transport (~1.7 mS cm -2 ). However, centimeter-scale Nafion|graphene|Nafion devices with several graphene domains show areal H + conductance of ~339 mS cm -2 and K + conductance of ~23.8 mS cm -2 (graphene conductance for H + is ~1735 mS cm -2 and for K + it is ~47.6 mS cm -2 ). Using a mathematical-transport-model and Nafion filled polycarbonate track etched supports, we systematically deconstruct the observed orders of magnitude increase in H + conductance for centimeter-scale CVD graphene. The mitigation of defects (>1.6 nm), wrinkles and tears via interfacial polymerization results in a conductance of ~1848 mS cm -2 for H + and ~75.3 mS cm -2 for K + (H + /K + selectivity of ~24.5) via intrinsic sub-nanometer proton selective defects in CVD graphene. We demonstrate atomically thin membranes with significantly higher ionic selectivity than state-of-the-art proton exchange membranes while maintaining comparable H + conductance. Our work provides a new framework to assess H + conductance and selectivity of large-area 2D membranes and highlights the role of intrinsic sub-nanometer proton selective defects for practical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Phenomenological Model of Nonlinear Dynamics and Deterministic Chaotic Gas Migration in Bentonite: Experimental Evidence and Diagnostic Parameters

Understanding gas migration in compacted clay materials, e.g., bentonite and claystone, is important for the design and performance assessment of an engineered barrier system of a radioactive waste repository system, as well as many practical applications. Existing field and laboratory data on gas migration processes in low-permeability clay materials demonstrate the complexity of flow and transport processes, including various types of instabilities, caused by nonlinear dynamics of coupled processes of liquid–gas exchange, dilation, fracturing, fracture healing, etc., which cannot be described by classical models of fluid dynamics in porous media. We here show that the complexity of gas migration processes can be explained using a phenomenological concept of nonlinear dynamics and deterministic chaos theory. To do so, we analyzed gas pressure and gas influx (i.e., input) and outflux (i.e., output), recorded during the gas injection experiment in the compact Mx80-D bentonite sample, and calculated a set of the diagnostic parameters of nonlinear dynamics and chaos, such a global embedding dimension, a correlation dimension, an information dimension, and a spectrum of Lyapunov exponents, as well as plotted 2D and 3D pseudo-phase-space strange attractors, based on the univariate influx and outflux time series data. These results indicate the presence of phenomena of low-dimensional deterministic chaotic behavior of gas migration in bentonite. In particular, during the onset of gas influx in the bentonite core, before the breakthrough, the development of gas flow pathways is characterized by the process of chaotic gas diffusion. After the breakthrough, with inlet-to-outlet movement of gas, the prevailing process is chaotic advection. During the final phase of the experiment, with no influx to the sample, the relaxation pattern of gas outflux is resumed back to a process of chaotic diffusion. The types of data analysis and a proposed phenomenological model can be used to establish the basic principles of experimental data-gathering, modeling predictions, and a research design.

36 MATERIALS SCIENCE↗

Advances in Nb 3 Sn superconducting radiofrequency cavities towards first practical accelerator applications

Abstract Nb 3 Sn is a promising next-generation material for superconducting radiofrequency cavities, with significant potential for both large scale and compact accelerator applications. However, so far, Nb 3 Sn cavities have been limited to continuous wave accelerating fields <18 MV m −1 . In this paper, new results are presented with significantly higher fields, as high as 24 MV m −1 in single cell cavities. Results are also presented from the first ever Nb 3 Sn-coated 1.3 GHz 9-cell cavity, a full-scale demonstration on the cavity type used in production for the European XFEL and LCLS-II. Results are presented together with heat dissipation curves to emphasize the potential for industrial accelerator applications using cryocooler-based cooling systems. The cavities studied have an atypical shiny visual appearance, and microscopy studies of witness samples reveal significantly reduced surface roughness and smaller film thickness compared to typical Nb 3 Sn films for superconducting cavities. Possible mechanisms for increased maximum field are discussed as well as implications for physics of RF superconductivity in the low coherence length regime. Outlook for continued development is presented.

43 PARTICLE ACCELERATORS↗

Polymer Additive Manufacturing for Marine Renewable Energy Applications: Best Practices, Research Trends, and Current Challenges

Additive manufacturing (AM) is a rapidly growing technology space, not only for prototyping, but is also becoming more feasible at larger scales and increasing component quantities. There are a large variety of AM processes and materials available to users and effectively applying those processes and materials to a specific use case can be challenging. One specific area where AM could be particularly beneficial is marine renewable energy (MRE). Not only is MRE a relatively nascent industry with a near-term need for rapid deployments and prototype testing, but developers could also see long-term benefits from the broad variety of environmentally resistant materials available and the ability to manufacture complex geometries that AM technologies offer. Over the past 4 years, AM materials have played an increasing role in the Advanced Materials project; a multi-year, multi-laboratory research project funded by the U.S. Department of Energy's Water Power Technologies Office, with the main goal of reducing barriers to the adoption of complex materials in the MRE industry. The primary focus of this project is to develop test methods and generate datasets to understand the long-term performance of advanced materials in marine environmental and address specific material challenges as they arise. This report provides an extensive overview of the research that has been performed specific to AM polymers as part of the Advanced Materials project. The intention of this document is to provide recommendations of best practices with regards to material selection, mechanical test method development, and design practices, lessons learned along the way, current research trends, and ongoing challenges with regards to AM polymers in marine environments. In particular, this report focuses on several key aspects: Material and process selection, Environmental conditioning and subsequent degradation quantification through mechanical characterization, Composite reinforcements on AM polymer substrates, Adhesion of instrumentation for mechanical characterization and loads measurements, Protective coatings for preventing biofouling and water ingress, Other MRE case studies where AM has proved particularly useful. Ultimately, we hope that the test methods that have been developed, data generated, and lessons learned from this research will be valuable to the MRE community (researchers and developers alike), as well as other industries, and can be used as a reference point as the respective MRE and AM industries continue to grow and mature.

16 TIDAL AND WAVE POWER↗

Investigation and Suppression of Oxygen Release by LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cathode under Overcharge Conditions

The safety issue of lithium-ion batteries is a crucial factor limiting their large-scale application. Therefore, it is of practical significance to evaluate the impact of their overcharge behavior because of the severe levels of oxygen release of cathode materials during this process. Here, by combining a variety of in situ techniques of spectroscopy and electron microscopy, this work studies the structural degradation of LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) accompanying the oxygen release in the overcharge process. It is observed that a small amount of O 2 evolves from the initial surface at ≈4.7V. When charging to a higher voltage (≈5.5V), a large amount of O 2 evolves on the newly formed surface due to the occurrence of microcracks. Based on experimental results and theoretical calculations, it is determined that the oxygen release mainly occurs in the near-surface regions, where the remaining oxygen vacancies accumulate to create voids. To suppress the oxygen release, single-crystalline NCM811 with integrated structure is introduced and serves as a cathode, which can effectively inhibit morphology destruction and reduce the activation of lattice oxygen in the surface region. These findings provide a theoretical basis and effective strategy for improving the safety performance of Ni-rich cathode materials in practical applications.

25 ENERGY STORAGE↗

Editorial: Particulate Matter Emissions From Conventional and Reformulated Fuel Combustion: Advances in Experiments and Simulations

Particulate matter (PM or soot) emissions generated by combustion of conventional and reformulated fuels adversely impact the environment and human health (Bond et al., 2013; Landrigan et al., 2018; World Health Organization (WHO), 2016), generating public awareness and motivating efforts towards the mitigation of their harmful effects. Soot formation is one of the most complex phenomena in combustion, involving interactions between combustion chemistry, fluid mechanics, mass/heat transport, and particle dynamics, spanning different spatial and temporal scales. A fundamental understanding of soot formation process is thus necessary to achieve a strong reduction of PM emissions and design cleaner and more efficient combustion systems. This has motivated a longstanding and ongoing research activity aimed at improving our understanding of the physical and chemical processes involved in soot formation, well reviewed in these recent works (Wang and Chung, 2019; Michelsen et al., 2020; Martin et al., 2022). Despite the wide interest, the transition from gas-phase molecules to incipient soot particles is still elusive and the successive particle growth and oxidation processes are far from being fully understood, especially in conditions relevant to real-world applications. Recent advances in combustion PM emission diagnostic and computational capabilities helped in improving the predictability of fundamental chemical and aerosol models for practical applications, thus tackling some of the above-mentioned challenges. The aim of this research topic is to display the ongoing research efforts in addressing the existing gaps on particulate formation from various fuel sources and in conditions typical of practical combustion applications (e.g. flames, engines, pool fires), through both experimental and numerical approaches.

42 ENGINEERING↗

Functional CeO x nanoglues for robust atomically dispersed catalysts

Single-atom catalysts make exceptionally efficient use of expensive noble metals and can bring out unique properties. However, applications are usually compromised by limited catalyst stability, which is due to sintering. Although sintering can be suppressed by anchoring the metal atoms to oxide supports, strong metal–oxygen interactions often leave too few metal sites available for reactant binding and catalysis, and when exposed to reducing conditions at sufficiently high temperatures, even oxide-anchored single-atom catalysts eventually sinter. Here we show that the beneficial effects of anchoring can be enhanced by confining the atomically dispersed metal atoms on oxide nanoclusters or ‘nanoglues’, which themselves are dispersed and immobilized on a robust, high-surface-area support. We demonstrate the strategy by grafting isolated and defective CeO x nanoglue islands onto high-surface-area SiO 2 ; the nanoglue islands then each host on average one Pt atom. Further, we find that the Pt atoms remain dispersed under both oxidizing and reducing environments at high temperatures, and that the activated catalyst exhibits markedly increased activity for CO oxidation. We attribute the improved stability under reducing conditions to the support structure and the much stronger affinity of Pt atoms for CeO x than for SiO 2 , which ensures the Pt atoms can move but remain confined to their respective nanoglue islands. The strategy of using functional nanoglues to confine atomically dispersed metals and simultaneously enhance their reactivity is general, and we anticipate that it will take single-atom catalysts a step closer to practical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-Performance InZn Alloy Anodes toward Practical Aqueous Zinc Batteries

Aqueous Zn batteries have high safety, low-cost and potential of delivering comparable energy density to alkali-ion batteries. However, its practical application is largely hampered by the limited cycle life associated with Zn anodes under conditions of high depth of discharge and high plating current densities. In this work, we report on electrodeposited indium-zinc alloy anodes that have well-dispersed zinc-domains surrounding indium domains that form a porous structure after dealloying which greatly improves tolerance to Zn dendrite formation. The InZn anodes exhibit low polarization of ~5 to 25 mV and demonstrate 700 cycles at a current density of ~10 mA cm -2 with a capacity of 5 mAh cm-2 capacity (45% depth-of-discharge). Full cells with an InZn anode, dibenzo[b,i]thianthrene-5,7,12,14-tetraone (DTT) cathode, in 2M ZnSO 4 deliver a capacity of ~ 110 mAh g -1 and good stability over 40 cycles. Finally, the work reveals a rational design of Zn-based anodes towards practical battery applications and opens the curtain for future development of aqueous Zn batteries.

25 ENERGY STORAGE↗

Strong tough hydrogels via the synergy of freeze-casting and salting out

Natural load-bearing materials like tendons possess high water content of ~70% but14 are still strong and tough even when used for over 1 million cycles per year, which is owed to the hierarchical assembly of anisotropic structures across multi-length-scales . In imitation of natural systems, various hydrogels have been created via methods like electro-spinning, extrusion, compositing, freeze casting, self-assembly, and mechanical stretching for improved mechanical performance. However, in contrast to tendons, many hydrogels with the same high water content do not show high strength, large toughness or high fatigue resistance. In this work, we present a strategy to produce strong, tough and fatigue resistant hydrogels with multi-length-scale hierarchical architecture using a freezing-assisted salting-out treatment. The produced exemplary poly(vinyl alcohol) hydrogels are highly anisotropic, comprising micrometer-scale honeycomb-like pore walls, which in turn comprise interconnected nanofibrils meshes, entirely physically assembled from polymer chains. These hydrogels are made of 70-95% water but can exhibit ultra-high ultimate stress (23.5 ± 2.7 MPa) and strain (2900 ± 450%), giant 32226 toughness (210 ± 13 MJ/m , 175 ± 8 kJ/m) and remarkable fatigue threshold (10.5 ± 1.3 kJ/m), which are 10 times tougher than natural tendon. The presented strategy could expand the applicability of weak polymeric material, like hydrogels, in practical applications that requires long-term services with high-loads and abrupt-impacts and extend the development of structural hydrogels.

36 MATERIALS SCIENCE↗

Improved Single-Ion Conductivity of Polymer Electrolyte via Accelerated Segmental Dynamics

Single-ion conducting polymer electrolytes (SICPEs) have many advantages for solid-state battery applications, while low conductivities remain the bottleneck for their practical applications. In this paper, a strategy that can significantly improve the ionic conductivity of SICPEs based on the concept of accelerated segmental dynamics was demonstrated by the evaluation of the thermal property, rheological behavior, morphology analysis, molecular dynamics simulation, and conductivity performance. With both “soft” poly(dimethylsiloxane) (PDMS) backbone and poly(ethylene glycol) (PEG) side chains, the obtained SICPE possesses faster segmental relaxation and higher lithium-ion conductivity. With lithium “transference” number close to unity, the obtained SICPE also shows excellent electrochemical stability against lithium metal electrodes. The clear relationship established between the segmental dynamics of polymer electrolyte and its ionic conductivity should contribute to achieve a solid electrolyte with improved ionic conductivity toward the next-generation solid-state battery.

Segmental Dynamics↗

Cybersecurity Considerations for Emerging Energy Technologies

AI, cloud computing, post-quantum cryptography, zero-trust architectures, microgrids, and virtual power plants. What do these things have in common? They are all emerging technologies in the clean energy space that will be a critical part of grid modernization efforts. As we work towards clean energy and decarbonization targets, these technologies, developed to solve real-world problems, will help us reach goals and achieve new efficiencies as the paradigm of grid operation shifts. However, there are growing concerns about the cybersecurity risks associated with these trending topics as they are used in critical infrastructure applications. This talk will cover gaps, challenges, and opportunities for the secure implementation of grid modernization solutions and novel energy applications of state-of-the-art networking and communications. Proactive risk mitigation strategies, including the application of cyber-informed engineering, will be discussed. Practical applications of these techniques will help provide countermeasures to the impact of cyberattacks on critical infrastructure technologies in a new, digitized grid landscape.

14 SOLAR ENERGY↗

Can Li: A Career in Catalysis

Prof. Can Li is distinguished for his seminal achievements in fundamental and applied researches in catalysis, especially in advancing the characterization of catalysts and catalytic reactions related to solar energy conversion and fine chemical synthesis. The scope of his research is wide ranging, and he is leading some of the fields. This account highlights his major scientific achievements in advancing the fundamental sciences of characterizing catalysts and understanding the mechanisms of catalytic reactions by developing in situ spectroscopic techniques (e.g., infrared (IR), ultraviolet (UV), Raman, space- and time-resolved spectroscopies and photoelectric imaging), and applying the obtained knowledge in the rational design and synthesis of catalysts for practical applications in photocatalytic, electrocatalytic and photoelectrocatalytic water splitting and CO 2 reduction, chiral synthesis in nanoreactors and ultradeep desulfurization of fuels, and fine chemical synthesis. In particular, his demonstration of the kiloton scale solar fuel production project will be introduced as a successful model for converting fundamental science into practical and impactful applications to convert CO 2 and water into solar fuels. This account also highlights his services to the catalysis communities and international collaborations for promoting catalysis science worldwide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sol-gel processing of a covalent organic framework for the generation of hierarchically porous monolithic adsorbents

Covalent organic frameworks (COFs) have emerged as a versatile material platform for such applications as chemical separations, chemical reaction engineering, and energy storage. Their inherently low mechanical stability, however, frequently renders existing methods of pelletization ineffective, contributing to pore collapse, pore blockage, or insufficient densification of crystallites. Here, we present a process for the shaping and densifying of COFs into robust centimeter-scale porous monoliths without the need for templates, additives, or binders. This process minimizes mechanical damage from shear-induced plastic deformation and further provides a network of interparticle mesopores that we exploit in accessing analyte capacities above those achievable from the intrinsic COF structure. Using a lattice-gas model, we accurately capture the monolithic structure across the mesoporous range and tie pore architecture to performance in both gas-storage and -separation applications. Collectively, these results represent a substantial step in the practical applicability of COFs and other mechanically weak porous materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A pseudo-two-dimensional (P2D) model for FeS 2 conversion cathode batteries

Conversion cathode materials are gaining interest for secondary batteries due to their high theoretical energy and power density. However, practical application as a secondary battery material is currently limited by practical issues such as poor cyclability. To better understand these materials, we have, for this study, developed a pseudo-two-dimensional model for conversion cathodes. We apply this model to FeS 2 – a material that undergoes intercalation followed by conversion during discharge. The model is derived from the half-cell Doyle–Fuller–Newman model with additional loss terms added to reflect the converted shell resistance as the reaction progresses. We also account for polydisperse active material particles by incorporating a variable active surface area and effective particle radius. Using the model, we show that the leading loss mechanisms for FeS 2 are associated with solid-state diffusion and electrical transport limitations through the converted shell material. The polydisperse simulations are also compared to a monodisperse system, and we show that polydispersity has very little effect on the intercalation behavior yet leads to capacity loss during the conversion reaction. Finally, we provide the code as an open-source Python Battery Mathematical Modeling (PyBaMM) model that can be used to identify performance limitations for other conversion cathode materials.

25 ENERGY STORAGE↗

Storm Surge Modeling as an Application of Local Time-Stepping in MPAS-Ocean

This paper presents the first practical application of local time-stepping (LTS) schemes in the Model for Prediction Across Scales-Ocean (MPAS-O). We use LTS schemes in a single-layer, global ocean model that predicts the storm surge around the eastern coast of the United States during Hurricane Sandy. The variable-resolution meshes used are of unprecedentedly high resolution in MPAS-O, containing cells as small as 125 m wide in Delaware Bay. It is shown that a particular, third-order LTS scheme (LTS3) produces sea-surface height solutions that are of comparable quality to solutions produced by the classical four-stage, fourth-order Runge-Kutta method (RK4) with a uniform time step on the same meshes. Furthermore, LTS3 is up to 35% faster in the best cases considered, where the number of cells using the coarse time-step relative to those using the fine time-step is as low as 1:1. This shows that LTS schemes are viable for use in MPAS-O with the added benefit of substantially less computational cost. The results of these performance experiments inform us of the requirements for efficient mesh design and configuration of LTS regions for LTS schemes. In particular, we see that for LTS to be efficient on a given mesh, it is important to have enough cells using the coarse time-step relative to those using the fine time-step, typically at least 1:5 to see an increase in performance.

54 ENVIRONMENTAL SCIENCES↗

High Energy Density Shape Memory Polymers Using Strain-Induced Supramolecular Nanostructures

Shape memory polymers are promising materials in many emerging applications due to their large extensibility and excellent shape recovery. However, practical application of these polymers is limited by their poor energy densities (up to ~1 MJ/m 3 ). Here, we report an approach to achieve a high energy density, one-way shape memory polymer based on the formation of strain-induced supramolecular nanostructures. As polymer chains align during strain, strong directional dynamic bonds form, creating stable supramolecular nanostructures and trapping stretched chains in a highly elongated state. Upon heating, the dynamic bonds break, and stretched chains contract to their initial disordered state. This mechanism stores large amounts of entropic energy (as high as 19.6 MJ/m 3 or 17.9 J/g), almost six times higher than the best previously reported shape memory polymers while maintaining near 100% shape recovery and fixity. The reported phenomenon of strain-induced supramolecular structures offers a new approach toward achieving high energy density shape memory polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optimizing dicyandiamide pretreatment conditions for enhanced structure and electronic properties of polymeric graphitic carbon nitride

Graphitic carbon nitride, a polymeric semiconductor, possesses a distinctive electronic band structure and exceptional chemical stability, making it a highly promising material for various catalytic applications such as electrocatalysis, photocatalysis, and photo-electrocatalysis. However, its practical applications remain limited due to its low active site density and poor electrical conductivity. In this study, to overcome such limitations, we have conducted a thorough investigation to explore the impact of dicyandiamide (DCDA) precursor pretreatment prior to thermal polymerization to graphitic carbon nitride. The DCDA precursor was subjected to various pretreatment methods including grinding using mortar and pestle, recrystallization through stirring or probe sonication after dissolving in deionized water, and freeze drying, prior to thermal polymerization at 550 °C for 2 hours. The structural and morphological properties of the catalysts prepared were compared and characterized by X-ray diffraction (XRD), attenuated total reflectance–Fourier transform infrared (ATR-IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) analysis while the electronic band gap properties were determined based on density functional theory (DFT) calculations for a set of crystalline systems having C/N ratios similar to those identified experimentally. In comparison to direct thermal polymerization, pretreated samples rendered the same product yield, diverse morphologies with flat or wrinkle structures, and reduced electrochemical resistance, making them suitable for use in various catalytic processes.

36 MATERIALS SCIENCE↗