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At least 199 records · Page 11

In situ XAS study of the local structure of the nano-Li 2 FeSiO 4 /C cathode

Despite the challenges in achieving its full theoretical capacity of reversible extraction of two Li ions, the Li 2 FeSiO 4 (LFS) cathode shows a remarkable cycling stability once its low electronic conductivity is addressed. By studying the local structure around the iron during electrochemical cycling using in situ x-ray absorption spectroscopy (XAS), it is possible to gain insight into the factors which determine the electrochemical properties of this material. In order to practically perform in situ XAS studies, the charge/discharge of LFS was maximized using two approaches: (a) reducing the particle size of LFS samples from micro-scale to nano-scale in order to reduce the diffusion path for intercalating ions; and (b) applying a conductive coating to each nanoparticle to facilitate electron transfer. A family of LFS materials was synthesized and characterized using x-ray diffraction, and scanning electron microscopy with energy dispersive analysis for structural and morphological analysis, as well as cyclic voltammetry and cycling tests for electrochemical performance diagnosis. This material was then characterized by in situ XAS. The results provide insight into the stable electrochemical performance of LFS and suggest new synthetic routes to reaching the theoretical capacity.

25 ENERGY STORAGE↗

Aqueous solution-based synthesis approach for carbon-disordered rocksalt composite cathode development and its limitations

Disordered rocksalt cathodes exhibit high specific capacities and high energy density; however, their low electronic conductivity poses a great challenge. Herein, we explored an aqueous-solution-based synthesis route that involves controlling the surface charges of Li 1.2 Mn 0.6 Ti 0.2 O 1.8 F 0.2 (LMTOF) to be anchored by a few-layer reduced graphene oxide (rGO) for the first time. The uniform rGO wrapping on the surface of the LMTOF particles is achieved by electrostatic attraction between the negatively charged rGO and positively charged LMTOF particles. Although the initial specific capacity of rGO-LMTOF composite increased by 58 % compared to the pristine LMTOF, the composite experienced a severe capacity fade over cycling. The synthesis process in an aqueous medium resulted in Li + /H + exchange and TM dissolution as evidenced from inductively coupled plasmon analysis and X-ray diffraction analysis. Therefore, this work suggests the search for alternative media or conditions for the synthesis of carbon-disordered rock salt cathode composite.

25 ENERGY STORAGE↗

Dendrite-free Al recycling via electrodeposition using ionic liquid electrolytes: The effects of deposition temperature and cathode surface roughness

In this report, the electrodeposition of Al from aluminum scrap alloys (A2020) on copper cathode substrates with varied surface roughness under different deposition temperatures was studied using low-temperature AlCl 3 -1-butyl-3-methyl-imidazolium chloride (BMIC) ionic liquid electrolytes. The bulk electrodeposition of Al was carried out under a voltage of 1.5 V at a stirring rate of 120 rpm using a fixed ionic liquid electrolyte concentration (molar ratio AlCl 3 : BMIC = 2:1). The effects of deposition temperature (range from 80 °C to 140 °C) and surface roughness of Cu cathode substrates (polished by 320, 600, 800, 1200 grits SiC sandpapers and mirror polishing process) on the morphology of deposited Al, current density, current efficiency and energy consumption, were investigated. The Al deposits were characterized using scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), profilometer, and electrochemical measurements for current density, current efficiency, and energy consumption. It is demonstrated that the deposition temperature and surface roughness of Cu electrodes play a critical role in the nucleation and growth of Al deposits. Higher deposition temperature promotes the diffusion and/or migration of Al 2 Cl 7 - ions and then enhances the current density and efficiency during the electrodeposition of Al. Smoother surface of Cu electrodes is preferred for the formation of dendrite-free Al deposits. Typically, on the mirror polished Cu electrode, no Al dendrite structure was observed, and only plate-like Al deposits were formed at the deposition temperature of 100 °C. Pure metallic Al was successfully deposited on Cu electrodes in AlCl 3 + BMIC ionic liquid electrolytes for all experiments with a current efficiency range from 72% to 99% and energy consumption of 4.6–6.3 kW h/kg Al.

54 ENVIRONMENTAL SCIENCES↗

Local structural investigation of non-crystalline materials at high pressure: the case of GeO 2 glass

Abstract Local structures play a crucial role in the structural polyamorphism and novel electronic properties of amorphous materials, but their accurate measurement at high pressure remains a formidable challenge. In this article, we use the local structure of network-forming GeO 2 glass as an example, to present our recent approaches and advances in high-energy x-ray diffraction, high-pressure x-ray absorption fine structure, and ab initio first-principles density functional theory calculations and simulations. Although GeO 2 glass is one of the best studied materials in the field of high pressure research due to its importance in glass theory and geophysical significance, there are still some long-standing puzzles, such as the existence of appreciable distinct fivefold [5] Ge coordination at low pressure and the sixfold-plus [6+] Ge coordination at ultrahigh pressure. Our work sheds light on the origin of pressure-induced polyamorphism of GeO 2 glass, and the [5] Ge polyhedral units may be the dominant species in the densification mechanism of network-forming glasses from tetrahedral to octahedral amorphous structures.

Physics↗

The surface triple-coupling on single crystalline cathode for lithium ion batteries

Single crystalline (SC) cathode materials, which are less susceptible to micro/nano-cracks formation and offer better structure stability compared to the polycrystalline counterpart, have attained great attention. However, the parasitic side reactions at the cathode-electrolyte interface induces the loss of active species, which consequently leads to continual degradation of the electrochemical performances. Herein, a triple coupling of concentration-gradient Na+, F- co-doping and surface NaF coating are exploited for the first time on SC LiNi 0.5C o 0.2 Mn 0.3 O 2 cathode by the hydrolysis of NaPF 6 . This process regulates the external structure of materials by constructing a “sandwich” configuration from surface to bulk: rock salt - mixing zone - layered phase. The detailed interface transformation mechanism is revealed by Neutron powder diffraction (NPD), spherical aberration corrected high-resolution scanning transmission electron microscopy (HR-STEM), electron energy loss spectroscopy (EELS), and Ar+ sputtering assisted X-ray photoelectron spectroscopy (XPS). The synergistic effects endow the SC cathode with outstanding capacity retentions: 91.3% at 25 °C and 85% at 45 °C, after 500 cycles at 5 C between 3.0 and 4.5 V. In addition, a high full-cell reversible capacity of 168.9 mAh g -1 with a capacity retention of 92.4% is achieved after 300 cycles at 1 C. Multiple characterizations further indicate that these superior results are mainly ascribed to the overall structure integrity of SC material, the thin cathode electrolyte interface, high content of lithium fluoride, and the low solubility of transition metal ions. This work opens a new avenue to construct a benign interface towards high-performance lithium ion batteries.

lithium ion batteries↗

Heterogenous activation of dynamic recrystallization and twinning during friction stir processing of a Cu-4Nb alloy

An interplay between high degree of shear deformation and deformation-induced heating occurs during friction stir processing (FSP) of metals. In medium-to-low stacking fault energy Cu alloys, this can lead to a complex spatially heterogenous activation of dynamic recrystallization (DRX) and twinning mechanisms. Within the Cu-Nb system, the presence of Nb is further expected to influence the DRX mechanism of the Cu matrix. However, the microstructural changes induced by the co-deformation of Nb during FSP are still not well understood. So, this study uses a combination of multimodal microstructural characterization, solution thermodynamics-based predictions, and computational crystal plasticity simulation to reveal the various microstructural evolution mechanisms that can occur during FSP of a Cu-4at.%Nb binary model alloy. The formation of softer DRX zones, and harder shear localization regions are revealed using electron backscatter diffraction, transmission electron microscopy, atom probe tomography, and crystal plasticity modeling.

36 MATERIALS SCIENCE↗

Multiple fermion scattering in the weakly coupled spin-chain compound YbAlO 3

The Heisenberg antiferromagnetic spin-1/2 chain, originally introduced almost a century ago, is one of the best studied models in quantum mechanics due to its exact solution, but nevertheless it continues to present new discoveries. Its low-energy physics is described by the Tomonaga-Luttinger liquid of spinless fermions, similar to the conduction electrons in one-dimensional metals. In this work we investigate the Heisenberg spin-chain compound YbAlO3 and show that the weak interchain coupling causes Umklapp scattering between the left- and right-moving fermions and stabilizes an incommensurate spin-density wave order at q = 2k F under finite magnetic fields. These Umklapp processes open a route to multiple coherent scattering of fermions, which results in the formation of satellites at integer multiples of the incommensurate fundamental wavevector Q = nq. Our work provides surprising and profound insight into bandstructure control for emergent fermions in quantum materials, and shows how neutron diffraction can be applied to investigate the phenomenon of coherent multiple scattering in metals through the proxy of quantum magnetic systems.

36 MATERIALS SCIENCE↗

Impact of nitrogen on lithium-induced corrosion and cracking of RAFM steel

The emergence of private fusion enterprises, combined with advancements in U.S. and EU ITER-TBM as well as EU DEMO liquid breeder blanket concepts, has renewed focus on the materials challenges. This study examines the compatibility of reduced activation ferritic/martensitic (RAFM) steel in liquid Lithium (Li) containing various Nitrogen (N) concentrations, tested at 600 and 700 °C for 500 and 1000 h under static conditions. Microstructural characterization revealed the corrosion-induced dissolution and precipitation in Li containing 0.082 and 0.17 wt.% N at 600 °C, while limited dissolution and precipitation were observed in N-gettered Li using zirconium (Zr) and titanium (Ti) foils at 600 °C. Tensile testing at room temperature after Li exposure revealed a decrease in strength and ductility of the RAFM steel as a function of N content in Li. Severe embrittlement was observed after 500 h in Li containing 0.17 wt.% N at 600 °C and after 500 h in hot-gettered Li at 700 °C. Chromium (Cr) depletion from the steel matrix was observed, leading to the formation of M6C-type carbides on the surface identified by electron microscopy (SEM), X-ray diffraction (XRD), in agreement with thermodynamic calculations. These findings highlight the critical materials challenges posed by liquid Li breeder blanket concepts, emphasizing the need for improved strategies to address Li-induced dissolution, precipitation, and steel embrittlement due to N contamination of the coolant.

Romedenne, Marie [ORNL] (ORCID:0000000317936561)↗

Hydrogen Storage Performance of Preferentially Oriented Mg/rGO Hybrids

Chemical interactions on the surface of a functional nanoparticle are closely related to its crystal facets, which can regulate the corresponding energy storage properties like hydrogen absorption. In this study, we reported a one-step growth of magnesium (Mg) particles with both close- and nonclose-packed facets, that is, {0001} and {$2\overline{116}$} planes, on atomically thin reduced graphene oxide (rGO). The detailed microstructures of Mg/rGO hybrids were revealed by X-ray diffraction, selected-area electron diffraction, high-resolution transmission electron microscopy, and fast Fourier transform analysis. Hydrogen storage performance of Mg/rGO hybrids with different orientations varies: Mg with preferential high-index {$2\overline{116}$} crystal surface shows remarkably increased hydrogen absorption up to 6.2 wt % compared with the system exposing no preferentially oriented crystal surfaces showing inferior performance of 5.1 wt % within the first 2 h. First-principles calculations revealed improved hydrogen sorption properties on the {$2\overline{116}$} surface with a lower hydrogen dissociation energy barrier and higher stability of hydrogen atoms than those on the {0001} basal plane, supporting the hydrogen uptake experiment. In addition, the hydrogen penetration energy barrier is found to be much lower than that of {0001} because of low surface atom packing density, which might be the most critical process to the hydrogenation kinetics. Here, the experimental and calculation results present a new handle for regulating the hydrogen storage of metal hydrides by controlled Mg facets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Decoupling Li out-diffusion and surface diffusion in the lithiation-assisted epitaxial growth of lithium tungstate

Lithiation-assisted epitaxy offers a flexible and robust approach for synthesizing high-quality Li-containing materials and interfaces with precise control. Here, in this study, we use lithium tungstate (Li x WO 3+x/2 , where x = 0 to 2) as a model system to investigate the intertwined effects of Li out-diffusion-induced compositional changes and surface-diffusion-induced morphological changes. By systematically varying synthesis and processing conditions, we uncover their impact on lithium tungstate film formation. Comprehensive characterizations, including X-ray diffraction, atomic force microscopy, X-ray photoemission spectroscopy and time-of-flight secondary ion mass spectrometry, reveal that low-temperature growth (< 300 °C) followed by high-temperature annealing yields continuous lithium tungstate films with significantly reduced surface roughness. In contrast, high-temperature deposition (≥ 300 °C) accelerates surface diffusion and Li out-diffusion, leading to island formation. Furthermore, in situ scanning transmission electron microscopy demonstrates the beam sensitivity of Li 2 WO 4 and reveals a phase transition from Li 2 WO 4 to LiWO 3.5 under prolonged electron beam exposure. These findings deepen our understanding of how to control composition and morphology of Li-containing films, providing valuable insights for the design and integration of energy materials.

Shi, Jueli [Pacific Northwest National Laboratory ↗

Femtosecond damage experiments and modeling of broadband mid-infrared dielectric diffraction gratings

High peak and average power lasers with high wall-plug efficiency, like the Big Aperture Thulium (BAT) laser, have garnered tremendous attention in laser technology. To meet the requirements of the BAT laser, we have developed low-dispersion reflection multilayer dielectric (MLD) gratings suitable for compression of high-energy pulses for operations at 2 micron wavelength. We carried out 10000-on-1 damage tests to investigate the fluence damage thresholds of the designed MLD gratings and mirrors, which were found between 100-230 mJ/cm 2 . An ultrashort pulsed laser (FWHM = 53 fs, λ = 1.9 μ m) operating at 500 Hz was used in the serpentine raster scans. The atomic force microscope images of the damage sites show blister formation of the underlying layers at lower fluences but ablation of the grating pillars at higher fluences. We simulated the dynamic electronic excitation in the MLD optics with a finite-difference in the time domain approach in 2D. The simulation results agree well with the LIDT measurements and the observed blister formation. This model is able to evaluate the absolute LIDT of MLD gratings.

42 ENGINEERING↗

Bismuth Subcarbonate Decorated Reduced Graphene Oxide Nanocomposite for the Sensitive Stripping Voltammetry Analysis of Pb(II) and Cd(II) in Water

In this paper, bismuth subcarbonate (BiO)2CO3-reduced graphene oxide nanocomposite incorporated in Nafion matrix ((BiO)2CO3-rGO-Nafion) was synthesized and further applied, for the first time, in the sensitive detection of Pb(II) and Cd(II) by square-wave anodic stripping voltammetry (SWASV). The as-synthesized nanocomposites were characterized by energy-dispersive spectroscopy (EDS), Raman spectroscopy, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). (BiO)2CO3 composite plays a key role in the improvement of the detection sensitivity, which can form multicomponent alloy with cadmium and lead. Additionally, the unique structure of rGO can enlarge the surface area and provide abundant active sites. Moreover, Nafion incorporation in the nanocomposite can effectively increase the adhesion and mechanical strength of the film, and further improve the preconcetration ability due to the cation-exchange capacity of its abundant sulfonate groups. As expected, the (BiO)2CO3-rGO/Nafion nanocomposite-modified glassy carbon electrode ((BiO)2CO3-rGO-Nafion/GCE) achieved low detection limits of 0.24 μg/L for Pb(II) and 0.16 μg/L for Cd(II), in the linear range of 1.0–60 μg/L, and showed some excellent performance, such as high stability, good selectivity, and sensitivity. Finally, synthetic water samples were prepared and further used to verify the practicability of the (BiO)2CO3-rGO-Nafion/GCE with satisfactory results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanochemical Synthesis of Sustainable Ternary and Quaternary Nanostructured Cu2SnS3, Cu2ZnSnS4, and Cu2ZnSnSe4 Chalcogenides for Thermoelectric Applications

Copper-based chalcogenides have emerged as promising thermoelectric materials due to their high thermoelectric performance, tunable transport properties, earth abundance and low toxicity. We have presented an overview of experimental results and first-principal calculations investigating the thermoelectric properties of various polymorphs of Cu2SnS3 (CTS), Cu2ZnSnS4 (CZTS), and Cu2ZnSnSe4 (CZTSe) synthesized by high-energy reactive mechanical alloying (ball milling). Of particular interest are the disordered polymorphs of these materials, which exhibit phonon-glass–electron-crystal behavior—a decoupling of electron and phonon transport properties. The interplay of cationic disorder and nanostructuring leads to ultra-low thermal conductivities while enhancing electronic transport. These beneficial transport properties are the consequence of a plethora of features, including trap states, anharmonicity, rattling, and conductive surface states, both topologically trivial and non-trivial. Based on experimental results and computational methods, this report aims to elucidate the details of the electronic and lattice transport properties, thereby confirming that the higher thermoelectric (TE) performance of disordered polymorphs is essentially due to their complex crystallographic structures. In addition, we have presented synchrotron X-ray diffraction (SR-XRD) measurements and ab initio molecular dynamics (AIMD) simulations of the root-mean-square displacement (RMSD) in these materials, confirming anharmonicity and bond inhomogeneity for disordered polymorphs.

36 MATERIALS SCIENCE↗

Synthesis and Characterization of Silver-Modified Nanoporous Silica Materials for Enhanced Iodine Removal

In aquatic environments, the presence of iodine species, including radioactive isotopes like 129 I and I 2 , poses significant environmental and health concerns. Iodine can enter water resources from various sources, including nuclear accidents, medical procedures, and natural occurrences. To address this issue, the use of natural occurring nanoporous minerals, such as zeolitic materials, for iodine removal will be explored. This study focuses on the adsorption of iodine by silver-modified zeolites (13X-Ag, 5A-Ag, Chabazite-Ag, and Clinoptilolite-Ag) and evaluates their performance under different conditions. All materials were characterized using scanning electron microscopey (SEM), energy-dispersive X-ray spectroscopy (EDS), powdered X-ray diffraction (P-XRD), Fourier-transform infrared spectrometry (FTIR), and nitrogen adsorption studies. The results indicate that Chabazite-Ag exhibited the highest iodine adsorption capacity, with an impressive 769 mg/g, making it a viable option for iodine removal applications. 13X-Ag and 5A-Ag also demonstrated substantial adsorption capacities of 714 mg/g and 556 mg/g, respectively, though their behavior varied according to different models. In contrast, Clinoptilolite-Ag exhibited strong pH-dependent behavior, rendering it less suitable for neutral to slightly acidic conditions. Furthermore, this study explored the impact of ionic strength on iodine adsorption, revealing that Chabazite-Ag is efficient in low-salinity environments with an iodine adsorption capacity of 51.80 mg/g but less effective in saline conditions. 5A-Ag proved to be a versatile option for various water treatments, maintaining its iodine adsorption capacity across different salinity levels. In contrast, Clinoptilolite-Ag exhibited high sensitivity to ionic competition, virtually losing its iodine adsorption ability at a NaCl concentration of 0.1 M. Kinetic studies indicated that the pseudo-second-order model best describes the adsorption process, suggesting chemisorption mechanisms dominate iodine removal. Chabazite-Ag exhibited the highest initial adsorption rate with a k 2 value of 0.002 mg g -1 h -1 , emphasizing its superior adsorption capabilities. Chabazite and Clinoptilolite, naturally occurring minerals, provide eco-friendly solutions for iodine adsorption. Chabazite superior iodine removal highlights its value in critical applications and its potential for addressing pressing environmental challenges.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Complex magnetic properties associated with competing local and itinerant magnetism in \({\text {Pr}}_2 {\text {Co}}_{0.86} {\text {Si}}_{2.88}\)

Ternary intermetallic compound \({\text {Pr}}_2 {\text {Co}}_{0.86} {\text {Si}}_{2.88}\) has been synthesized in single phase and characterized by x-ray diffraction, scanning electron microscopy with energy dispersive x-ray spectroscopy (SEM-EDX) analysis, magnetization, heat capacity, neutron diffraction and muon spin rotation/relaxation ( \(\mu\) SR) measurements. The polycrystalline compound was synthesized in single phase by introducing necessary vacancies in Co/Si sites. Magnetic, heat capacity, and zero-field neutron diffraction studies reveal that the system undergoes magnetic transition below \(\sim\) 4 K. Neutron diffraction measurement further reveals that the magnetic ordering is antiferromagnetic in nature with an weak ordered moment. The high temperature magnetic phase has been attributed to glassy in nature consisting of ferromagnetic clusters of itinerant (3 d ) Co moments as evident by the development of internal field in zero-field \(\mu\) SR below 50 K. The density-functional theory (DFT) calculations suggest that the low temperature magnetic transition is associated with antiferromagnetic coupling between Pr 4 f and Co 3 d spins. Pr moments show spin fluctuation along with unconventional orbital moment quenching due to crystal field. The evolution of the symmetry and the crystalline electric field environment of Pr-ions are also studied and compared theoretically between the elemental Pr and when it is coupled with other elements such as Co. The localized moment of Pr 4 f and itinerant moment of Co 3 d compete with each other below \(\sim\) 20 K resulting in an unusual temperature dependence of magnetic coercivity in the system.

36 MATERIALS SCIENCE↗

Exploring the $A$-V-Sb landscape beyond $A$$\mathrm{V_3}$ $\mathrm{Sb_5}$: A case study on the $\mathrm{KV_6}$ $\mathrm{Sb_6}$ Kagome compound

Kagome compounds have garnered attention in the past few years for their intriguing magnetic properties arising from spin frustration dictated by the geometry of the Kagome sublattice. In this paper, we highlight the success of the unconventional hydride route for the fast and easy synthesis of the Kagome compound $\mathrm{KV_6}$ $\mathrm{Sb_6}$. Here, high-temperature in situ powder x-ray diffraction (PXRD) studies proved to be useful in hinting at the existence of $\mathrm{KV_6}$ $\mathrm{Sb_6}$, identifying its synthesis conditions, and understanding the reaction mechanism. The crystal structure for $\mathrm{KV_6}$ $\mathrm{Sb_6}$ was determined from high-resolution PXRD data. The compound has a layered structure [$R\overline{3}m, a = 5.5318$ (9) Å, $c = 34.23$ (3)Å 3 $Z = 3$] at room temperature] and features a Kagome bilayer of V atoms. $\mathrm{KV_6}$ $\mathrm{Sb_6}$ is isostructural to the previously reported $\mathrm{RbV_6}$ $\mathrm{Sb_6}$ and $\mathrm{CsV_6}$ $\mathrm{Sb_6}$ compounds. $\mathrm{KV_6}$ $\mathrm{Sb_6}$ is thermally stable in vacuum up to 1173 K, as evident from the high-temperature in situ PXRD and differential scanning calorimetric analysis. Investigation of magnetic properties for $\mathrm{KV_6}$ $\mathrm{Sb_6}$ between 2 and 300 K reveals temperature-independent paramagnetism and an absence of superconductivity, like the Rb and Cs analogs. Furthermore, we compare the magnetic properties of K V 3 Sb 5 , another ternary Kagome compound, synthesized via two different methods: the hydride route and the traditional route from elements. Low-temperature transport property measurements of $\mathrm{KV_6}$ $\mathrm{Sb_6}$ indicate metallic behavior and an intrinsically low thermal conductivity of $\mathrm{1.0 W K^-1}$ $\mathrm{m^-1}$ at 300 K. The layered structure of $\mathrm{KV_6}$ $\mathrm{Sb_6}$ makes it an attractive candidate for deintercalation and doping studies to tune both magnetic and transport properties, laying a foundation for further studies.

36 MATERIALS SCIENCE↗

Molecular beam epitaxy of GaAs templates on water soluble NaCl thin films

Expensive III-V substrates are cost limiting for the adoption of many technologies. Consequently, being able to reuse the original substrate is highly desirable. Existing substrate reuse techniques have significant drawbacks, but this work discusses a new method using molecular beam epitaxy deposition of water soluble NaCl thin films on commonly employed (0 0 1) GaAs substrates. Single-crystal GaAs templates are grown on continuous NaCl layers utilizing careful exposure of the NaCl to an in-situ electron beam and a low temperature nucleation layer. The template layers can be quickly removed from the substrate via dissolution of the NaCl. After liftoff, the original wafer shows an increase in rms surface roughness of only 0.2 nm.

14 SOLAR ENERGY↗