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At least 775 records · Page 43

Insight of Synthesis of Single Crystal Ni-Rich LiNi 1-x-y Co x Mn y O 2 Cathodes

Single-crystal Ni-rich LiNi 1-x-y Co x Mn y O 2 (NCM) cathodes have garnered widespread attention in the lithium-ion battery community due to their unique advantages in mechanical performance and their ability to minimize interfacial electrochemical side reactions. The synthesis of single-crystal materials with monodisperse and appropriate size, minimal lattice defects, and highly ordered structures is the key for high-performance batteries. However, achieving this goal poses challenges due to the lack of in-depth understanding regarding specific experimental parameters and the solid reaction mechanism during the synthesis process. Further, in this review, the aim is to provide an in-depth analysis of the critical process parameters involved in the synthesis and their impact on crystal morphology, structure, and electrochemical performance. Consequently, the first section focuses on the effect of the precursor morphology, lithium salt, atmosphere, and sintering procedure. In the second section, the study delves into an in-depth discussion of the solid reaction and crystal growth mechanism. Lastly, it is concluded by highlighting the prospects and challenges associated with the synthesis and application of single-crystal Ni-rich NCM cathodes.

25 ENERGY STORAGE↗

Ionic conductive polymers as artificial solid electrolyte interphase films in Li metal batteries – A review

Lithium (Li) metal has been considered as the ultimate anode material for next-generation rechargeable batteries due to its ultra-high theoretical specific capacity (3860 mAh g -1 ) and the lowest reduction voltage (-3.04 V vs the standard hydrogen electrode). However, the dendritic Li formation, uncontrolled interfacial reactions, and huge volume variations lead to unstable solid electrolyte interphase (SEI) layer, low Coulombic efficiency and hence short cycling lifetime. Designing artificial solid electrolyte interphase (artificial SEI) films on the Li metal electrode exhibits great potential to solve the aforementioned problems and enable Li–metal batteries with prolonged lifetime. Polymer materials with good ionic conductivity, superior processability and high flexibility are considered as ideal artificial SEI film materials. In this review, according to the ionic conductive groups, recent advances in polymeric artificial SEI films are summarized to afford a deep understanding of Li ion plating/stripping behavior and present design principles of high-performance artificial SEI films in achieving stable Li metal electrodes. Perspectives regarding to the future research directions of polymeric artificial SEI films for Li–metal electrode are also discussed. The insights and design principles of polymeric artificial SEI films gained in the current review will be definitely useful in achieving the Li–metal batteries with improved energy density, high safety and long cycling lifetime toward next-generation energy storage devices.

25 ENERGY STORAGE↗

Advanced Analysis of X-ray Fluorescence Measurements of the Interfacial Density of Eu Ions at Liquid–Liquid Interfaces for Solvent Back-Extraction

X-ray fluorescence near total reflection (XFNTR) is the primary technique used to measure the element-specific interfacial density of ions at liquid−liquid interfaces. Fluorescence from ions in the bulk liquids can complicate the determination of the interfacial density; consequently, measurements have been previously limited to samples without ions in the upper phase and with concentrations on the order of 10 μM or less in the lower phase. We modify the analysis of XFNTR data to account for ions in both bulk phases, then demonstrate its use in the context of rare-earth separations processes. In a model of ion stripping (i.e., back-extraction), dodecane solutions of di(2-ethylhexyl)- phosphoric acid (HDEHP) loaded with Eu(III) at the 1 mM level are placed in contact with either pure water or aqueous solutions of nitric or citric acid at pH 3. XFNTR measurements of equilibrated, quiescent samples reveal that citric acid solutions produce a disproportionately large depletion of ions from the interface compared to that from the bulk organic solution, whereas stripping by pure water or nitric acid solutions is negligible. As a result, this advance in the methodology of XFNTR may have broad applicability to the investigation of metal ions in chemical and biological processes at liquid−liquid interfaces.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Iron-Doped Sodium Vanadium Oxyflurophosphate Cathodes for Sodium-Ion Batteries—Electrochemical Characterization and In Situ Measurements of Heat Generation

Sodium-ion batteries (NaIBs) are increasingly being envisioned for grid-scale energy-storage systems because of cost advantages. However, implementation of this vision has been challenged by the low-energy densities delivered by most NaIB cathodes. Toward addressing this challenge, the authors report the synthesis and characterization of a new iron-doped Na 3 Fe 0.3 V 1.7 O(PO 4 ) 2 F 2 cathode using a novel facile hydrothermal route. The synthesized material was characterized using scanning electron microscopy, X-ray diffraction, and Mössbauer spectroscopy techniques. The obtained discharge capacity in the half-cell configuration lies from 119 to 125 to 130 mA h/g at C/10 while tested using three different electrolyte formulations, dimethyl carbonate–ethylene carbonate (EC)–propylene carbonate (PC), diethyl carbonate–EC, and EC–PC, respectively. The synthesized cathodes were also evaluated in full-cell configurations, which delivered an initial discharge capacity of 80 mA h/g with NaTi 2 (PO 4 ) 3 MWCNT as the anode. Ionic diffusivity and interfacial charge transfer kinetics were also evaluated as a function of temperature and sodium concentration, which revealed that electrochemical rate performances in this material were limited by charge-transfer kinetics. To understand the heat generation mechanism of the Na/Na 3 Fe 0.3 V 1.7 O(PO 4 ) 2 F 2 half-cell during charge and discharge processes, an electrochemical isothermal calorimetry measurement was carried out at different current rates for two different temperatures (25 and 45 °C). The results showed that the amount of heat generated was strongly affected by the operating charge/discharge state, C-rate, and temperature. Altogether, this work provides a new synthesis route for the development of iron-doped Na 3 Fe 0.3 V 1.7 O(PO 4 ) 2 F 2 -based high-performance sodium cathode materials aimed at providing a viable pathway for the development and deployment of large-scale energy-storage based on sodium battery systems.

25 ENERGY STORAGE↗

Improved Mechanical Adhesion Enabled by Bilayer Hole Transport Layers in Perovskite Solar Cells

We investigate buried-interface mechanical integrity in metal-halide perovskite half-cells using carbazole-based self-assembled monolayers (SAMs) and bilayer hole transport layers composed of metal oxide underlayers and SAMs. Combining macroscopic and microscopic characterization, we quantify interfacial fracture energy (Gc) and identify delamination pathways. SAM deposition on NiOx increases Gc by approximately 10-fold compared with ITO, highlighting the importance of oxide underlayer selection. To isolate the effect of removing noncovalently bonded SAM molecules, we use vapor-deposited perovskite as a solvent-free model system, decoupling the rinse step inherent to solution processing. Removing loosely bound SAM molecules increases Gc from 0.94 +- 0.08 J.m-2 to 4.82 +- 0.79 J.m-2. These results show that oxide selection and SAM binding quality are both critical for strengthening buried interfaces and designing mechanically robust perovskite solar cells.

14 SOLAR ENERGY↗

Two-Phase Fluid Flow Properties of Rough Fractures With Heterogeneous Wettability: Analysis With Lattice Boltzmann Simulations

Fractures are conduits for fluid flow in low-permeability geological formations. Multiphase flow properties of fractures are important in natural processes and in engineering applications such as the evaluation of the sealing capacity of caprocks and productivity of hydrocarbon-bearing tight rocks. Investigations of flow and transport through fractures typically focus on the effects of fracture geometric and mechanical factors such as aperture, roughness, and compressibility. The wettability of the fracture surfaces and its influence on microscale interfacial phenomena and macroscale effective transport properties are seldom studied. In this study, we investigated the effect of heterogeneous wetting properties on the displacement of water by supercritical CO2 through a series of lattice Boltzmann method simulations. The results show the evolution of the CO2 plume within a fracture is controlled by both the roughness of the aperture field and the wetting distribution. We combined these factors into a capillary pressure map that can be related to the macroscopic flow behavior of the fracture. We observed that heterogeneous wetting distributions promote the residual trapping of water where lower capillary pressures allowed for isolated water pockets in higher capillary pressure zones. Analysis of fracture unsteady relative permeability shows the effect of wetting on permeability evolution and provides support for the viscous-coupling relative permeability model. Finally, analysis of the steady-state relative permeability and saturation demonstrates a strong correlation between permeability and the standard deviation of the capillary pressure field. Thus, characterizing the distribution of wetting properties of fractures is crucial to understanding multiphase fracture flow and transport properties.

58 GEOSCIENCES↗

Influence of surface chemistry on Li nucleation energetics on graphene-based surfaces

Lithium metal is a promising high-capacity anode material for solid-state batteries, but it typically suffers from poor cyclability. Carbon scaffold hosts have the potential to improve this performance due to their high electronic conductivity and large surface area, which facilitates lithium-ion adsorption and desorption. Scaffold surface chemistry is known to significantly influence performance outcomes, but the details of these interactions are not fully understood. Here, this study employs first-principles simulations to explore lithium transport and nucleation on graphene anodes with various surface chemistries. Using enhanced sampling techniques, ab initio molecular dynamics, and density functional theory calculations, we find that although surface chemistry has a minimal impact on lithium interfacial transport, it influences surface nucleation significantly. Both heteroatom dopants and intrinsic defects lower the nucleation barrier, creating a more favorable environment for lithium nucleation compared to pristine graphene. In addition, our results reveal a complex interplay between surface lithium concentration, lithium transport, and nucleation kinetics. These findings highlight the potential of surface modifications to precisely control nucleation processes on carbon-based anodes and provide design guidance for reducing dendrite formation and improving the cycle life of solid-state batteries.

36 MATERIALS SCIENCE↗

Comprehensive Characterization of Multi-Phase Sulfurized Polyacrylonitrile Cathodes for Lithium-Sulfur Batteries

Sulfurized polyacrylonitrile (SPAN) is considered one of the most promising cathode materials to overcome the operational challenges that plague lithium-sulfur (Li-S) batteries. However, material properties and electrochemical performance implications of SPAN prepared under different synthesis conditions are not yet fully investigated. In this study, we show the impacts of different synthesis conditions on the formation of sulfur to PAN bonds and redox reaction mechanisms of multi-phase SPAN via comprehensive material and electrochemical characterizations. In-situ Raman analysis was first applied to study the multi-phase SPAN-based Li-S cells. We found that both elemental sulfur and chemically bonded sulfur are present under the synthesis condition of 300 degree C/3 h along with unreacted PAN. The incompletely sulfurized, multi-phase SPAN exhibited an unusually rapid capacity degradation in the resultant Li-S cells, which is attributed to polysulfide formation and continuously growing interfacial impedance in the Li-S cells. On the other hand, SPAN samples prepared under the synthesis condition of 350 degree C/3 h are found completely sulfurized with chemically bonded sulfur to the PAN backbone without the presence of free elemental sulfur. Complete sulfurization of SPAN led to exceptionally stable cycle performance due to excellent reversible redox processes of chemically bonded sulfur with Li+ in the Li-S cells.

DIRECT ENERGY CONVERSION,ENERGY STORAGE↗

Study of the kinetics and mechanism of the thermal nitridation of SiO2

X-ray photoelectron spectroscopy (XPS) has been used to study the nitridation time and temperature dependence of the nitrogen distribution in thermally nitrided SiO2 films. The XPS data show that the maximum nitrogen concentration near the (SiO(x)N(y)/Si interface is initially at the interface, but moves 20-25 A away from the interface with increasing nitridation time. Computer modeling of the kinetic processes involved is carried out and reveals a mechanism in which diffusing species, initially consisting primarily of nitrogen, react with the substrate, followed by formation of the oxygen-rich oxynitride due to reaction of the diffusing oxygen displaced by the slower nitridation of the SiO2. The data are consistent with this mechanism provided the influence of the interfacial strain on the nitridation and oxidation kinetics is explicitly accounted for.

Vasquez, R. P.↗

A Theoretical Study of Remobilizing Surfactant Retarded Fluid Particle Interfaces

Microgravity processes must rely on mechanisms other than bouyancy to move bubbles or droplets from one region to another in a continuous liquid phase. One suggested method is thermocapillary migration in which a temperature gradient is applied to the continuous phase. When a fluid particle contacts this gradient, one pole of the particle becomes warmer than the opposing pole. The interfacial tension between the drop or bubble phase and the continuous phase usually decreases with temperature. Thus the cooler pole is of higher interfacial tension than the warmer pole, and the interface is tugged in the direction of the cooler end. This thermocapillary or thermally induced Marangoni surface stress causes a fluid streaming in the continuous phase from which develops a viscous shear traction and pressure gradient which together propel the particle in the direction of the warmer fluid. In this paper, we provide a theoretical basis for remobilizing surfactant retarded fluid particle interfaces in an effort to make viable the use of thermocapillary migrations for the management of bubbles and drops in microgravity,

Wang, Yanping↗

Friction Stir Dovetailing of AA7099 to Steel with AA6061 Interlayer for Reduced Zn Embrittlement at Dissimilar Interface

Joining of high strength Al alloy (AA7099) to steel (rolled homogeneous armor) with and without AA6061 interlayer was achieved using a friction stir dovetailing (FSD) method. Detailed investigations were conducted to establish correlations between mechanical performance and microstructural evolution of FSD joints. Lap shear tensile testing revealed that incorporation of the AA6061 interlayer combined with tailored processing methodology significantly improved both mechanical interlocking and load transmission across the dovetail interface. Following incorporation of the interlayer, the maximum load carrying capacity and peak extension (of the AA7099/AA6061/steel joint) are 60% and 210% higher, respectively, than results obtained from an AA7099/steel joint without an interlayer. Without an AA6061 interlayer, formation of zinc rich intermetallic compounds led to brittle interfacial failure of the AA7099-steel FSD joint. Incorporation of novel tool and joint configuration eliminated asymmetric joint performance as a function of loading direction, which is generally observed in friction stir lap welding. The efficacy of the use of an AA6061 interlayer in joining AA7099 to steel was demonstrated through mechanical testing as well as high resolution analytical electron microscopy characterization.

Dissimilar metal joining, Friction stir dovetailin↗

Hierarchically Structured Vitrimer Biocomposites for Sustainable Manufacturing

Polymers containing dynamic covalent bonds (DCBs) exhibit thermoplastic-like flow above their topology freezing temperature (T v ) while maintaining thermoset-like properties below it, making them promising for sustainable manufacturing. However, their large-scale adoption remains limited due to challenges in accurately determining T v and achieving efficient fiber-matrix bonding in composite applications. Here, hierarchically structured epoxy-anhydride-based polyester vitrimer composites reinforced with cellulosic filaments is demonstrated, where hydroxyl groups on fiber surfaces participate directly in transesterification with the matrix. Further, this dynamic interfacial bonding delivers exceptional mechanical properties, including ≈70 MPa shear strength and >10% strain-to-failure, while enabling thermal malleability. Using a combination of nuclear magnetic resonance and nano-infrared spectroscopies, direct evidence is provided that chemical bond exchange begins well below the conventionally measured T v , supporting the hypothesis that rheologically determined T v reflects a combination of chemical exchange and frictional dynamics rather than a discrete transition. The composites demonstrate excellent processability through vacuum-assisted resin transfer molding and maintain >90% of their mechanical properties after multiple thermal reforming cycles. These findings advance both the fundamental understanding of vitrimeric transitions and the practical development of sustainable, high-performance composite materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomistic Origins of Reversible Noncatalytic Gas–Solid Interfacial Reactions

Noncatalytic gas-solid reactions are a large group of heterogeneous reactions that are usually assumed to occur irreversibly because of the strong driving force to favor the forward direction toward the product formation. Using the example of Ni oxidation into NiO with CO 2 , herein we demonstrate the existence of the reverse element that results in the NiO reduction from the countering effect of the gaseous product of CO. Using in-situ electron microscopy observations and atomistic modeling, we show that the oxidation process occurs via preferential CO 2 adsorption along step edges that results in step-flow growth of NiO layers, and the presence of Ni atoms on the flat NiO surface promotes the nucleation of NiO layers. Simultaneously, the NiO reduction happens via preferential step-edge adsorption of CO that leads to the receding motion of atomic steps, and the presence of Ni vacancies in the NiO surface facilitates the CO adsorption induced surface pitting. Based on the in-situ TEM observations, temperature and CO 2 pressure effect maps are constructed to illustrate the spatiotemporal dynamics of the competing NiO redox reactions. We report, these results demonstrate the rich gas-solid surface reaction dynamics induced by the co-existing forward and reverse reaction elements and have practical applicability in manipulating gas-solid reactions via controlling the gas environment or atomic structure of the solid surface to steer the reaction toward the desired direction.

25 ENERGY STORAGE↗

Single‐Step Recovery of Water from Stable Crude Oil‐Water Emulsion Using Surface Engineered Hybrid Inorganic‐Polymer Membranes

ABSTRACT Separating crude oil from water remains one of the most stubborn challenges in environmental remediation, especially for surfactant‐stabilized emulsions that resist conventional demulsification methods. Here, we report a scalable strategy for achieving near‐zero‐discharge separation of crude oil emulsions using a single superhydrophilic membrane. By applying low‐temperature atomic layer deposition (ALD) of various metal oxides onto activated polyvinylidene fluoride (PVDF) membranes, we create atomically precise surface‐engineered (SE) membranes that maintain an exceptionally strong hydration layer at the membrane‐feed interface, even at high oil loadings. Among the various metal oxides, TiO 2 ‐modified SE membranes exhibit superior interfacial water stability, enabling sustained dewatering of complex crude oil‐water emulsions with >98% separation efficiency and >97% water recovery, compared to only 24.6% water recovery for the pristine membrane. This separation performance surpasses conventional hydrophilic membranes and is comparable to complex Janus channel membrane systems, demonstrating near‐complete emulsion separation using a single membrane. This low‐temperature membrane surface engineering process with atomic‐level precision and potential for scalability via roll‐to‐roll fabrication is promising for industrial‐scale, energy‐efficient water treatment and oil spill remediation applications.

Sengupta, Bratin [Applied Materials Division Argon↗

Mechanisms of dissolution from gibbsite step edges elucidated by ab initio molecular dynamics with enhanced sampling

Surface reactions underpin our collective understanding of mineral dissolution. This impacts a range of predictive geochemical models (for weathering, the fate and transport of metals) as well as industrial utilization of minerals. Yet atomistic details are rarely known due to the complex mineral/fluid interfacial environment. There is significant need to understand the mechanistic details of dissolution reactions and how they depend on surface morphology and solution conditions. This work utilizes surface pit models in conjunction with changes to solution composition that mimic pH to explore surface detachment of aluminate from gibbsite, which is a primary source of Al in soils and within the industrial processing of aluminum. Ab initio molecular dynamics simulations with enhanced sampling has been used to explore the detailed process of the detachment, the results of which indicate two potential pathways that are differentiated based upon the extent of water hydration. Here, the heights of the energy barriers depend upon the local morphology which influence the number of bridges (quasi-)simultaneously broken (1 or 2) or the Al-O coordination of the neighboring aluminum atoms (5 or 6) at the armchair edge. pH effects are significant, with a nearly 50% reduction in barrier height under alkaline conditions that are relevant to geothermal fluids and Al extraction from minerals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrocatalysis in Alkaline Media and Alkaline Membrane-Based Energy Technologies

Hydrogen energy-based electrochemical energy conversion technologies offer the promise of enabling a transition of the global energy landscape from fossil fuels to renewable energy. Here, we present a comprehensive review of the fundamentals of electrocatalysis in alkaline media and applications in alkaline-based energy technologies, particularly alkaline fuel cells and water electrolyzers. Anion exchange (alkaline) membrane fuel cells (AEMFCs) enable the use of nonprecious electrocatalysts for the sluggish oxygen reduction reaction (ORR), relative to proton exchange membrane fuel cells (PEMFCs), which require Pt-based electrocatalysts. However, the hydrogen oxidation reaction (HOR) kinetics is significantly slower in alkaline media than in acidic media. Understanding these phenomena requires applying theoretical and experimental methods to unravel molecular-level thermodynamics and kinetics of hydrogen and oxygen electrocatalysis and, particularly, the proton-coupled electron transfer (PCET) process that takes place in a proton-deficient alkaline media. Extensive electrochemical and spectroscopic studies, on single-crystal Pt and metal oxides, have contributed to the development of activity descriptors, as well as the identification of the nature of active sites, and the rate-determining steps of the HOR and ORR. Among these, the structure and reactivity of interfacial water serve as key potential and pH-dependent kinetic factors that are helping elucidate the origins of the HOR and ORR activity differences in acids and bases. Additionally, deliberately modulating and controlling catalyst-support interactions have provided valuable insights for enhancing catalyst accessibility and durability during operation. The design and synthesis of highly conductive and durable alkaline membranes/ionomers have enabled AEMFCs to reach initial performance metrics equal to or higher than those of PEMFCs. We emphasize the importance of using membrane electrode assemblies (MEAs) to integrate the often separately pursued/optimized electrocatalyst/support and membranes/ionomer components. Operando/in situ methods, at multiscales, and ab initio simulations provide a mechanistic understanding of electron, ion, and mass transport at catalyst/ionomer/membrane interfaces and the necessary guidance to achieve fuel cell operation in air over thousands of hours. We hope that this Review will serve as a roadmap for advancing the scientific understanding of the fundamental factors governing electrochemical energy conversion in alkaline media with the ultimate goal of achieving ultralow Pt or precious-metal-free high-performance and durable alkaline fuel cells and related technologies.

30 DIRECT ENERGY CONVERSION↗

Mechanically and Thermally Enhanced 3D-Printed Photocurable Polymer Nanocomposites Containing Functionalized Chitin Nanowhiskers by Stereolithography

Additive manufacturing, or simply 3D printing (3DP), where objects are built through layer-wise material deposition, has gained significant academic and industrial attention as a result of the development of advanced and functional materials requiring rapid, customized, and flexible solutions. In the context of green manufacturing, diversifying environmentally and economically sustainable material portfolios is an essential endeavor for the success of 3DP technology that uses widely available, highly valuable, and renewable materials. Here, we used stereolithography (SLA) for processing methacrylate-based photocurable resins containing crab shell-derived chitin nanowhiskers (CNWs), which are surface-functionalized by reactive acrylate groups. Results from full spectral, thermal, structural, and topological analyses corroborate not only the surface functionalization of CNWs but also indicate the presence of these photocurable CNW (pCNW) fillers in the 3D-printed nanocomposites. Owing to the strong interfacial bond induced by the physical and chemical crosslinking between the pCNW and methacrylate (MA) polymer matrix, the internally formulated nanocomposites displayed enhanced thermomechanical properties (e.g., storage modulus and glass transition temperature) compared to those of commercially available pure SLA resins. For instance, the inclusion of 0.5 wt % pCNW improved the tensile strength and stiffness to up to 78 and 71%, respectively, without compromising the toughness and ductility of the printed material. Accordingly, this result also evidences the compatibility between the filler and resin materials. Consequently, the formation of a crosslinked network in the nanocomposite structure results in a higher thermal stability and activation energy (i.e., up to ~79%) for all the hybrid materials than the pristine MA. Finally, the high-resolution SLA print features, dimensional accuracy, and enhanced mechanical performance of our microstructure-forming functionalized chitin-based nanocomposites make them promising materials for a wide range of robust and high-performance industrial applications.

36 MATERIALS SCIENCE↗

1000 Wh L−1 lithium-ion batteries enabled by crosslink-shrunk tough carbon encapsulated silicon microparticle anodes

Abstract Microparticulate silicon (Si), normally shelled with carbons, features higher tap density and less interfacial side reactions compared to its nanosized counterpart, showing great potential to be applied as high-energy lithium-ion battery anodes. However, localized high stress generated during fabrication and particularly, under operating, could induce cracking of carbon shells and release pulverized nanoparticles, significantly deteriorating its electrochemical performance. Here we design a strong yet ductile carbon cage from an easily processing capillary shrinkage of graphene hydrogel followed by precise tailoring of inner voids. Such a structure, analog to the stable structure of plant cells, presents ‘imperfection-tolerance’ to volume variation of irregular Si microparticles, maintaining the electrode integrity over 1000 cycles with Coulombic efficiency over 99.5%. This design enables the use of a dense and thick (3 mAh cm–2) microparticulate Si anode with an ultra-high volumetric energy density of 1048 Wh L–1 achieved at pouch full-cell level coupled with a LiNi0.8Co0.1Mn0.1O2 cathode.

25 ENERGY STORAGE↗