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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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SEM images of MMOs derived from Mg–Al-acetate intercalated LDHs synthesized by acetamide hydrolysis with (a) Mg/Al = 3, (b) Mg/Al = 4 and their high temperature CO 2 capture capacity versus temperature (c) were obtained.
Fast charging of high-capacity anodes is challenging due to lithium plating reactions, which lead to poor cycling performance and safety concerns. Thus, accurate predictions of plating onset and an understanding of this electrochemical process are crucial for robust battery design. However, the most commonly used models, based on porous electrode theory (e.g., the pseudo-2D model), are notoriously difficult to calibrate due to their complexity, limiting their predictive power. This work studies the process of lithium plating during fast charging of (small-particle) graphite half-cells by measuring local reaction progression and plating behavior using optical operando techniques. These experiments employ a realistic 1D graphite electrode geometry with commercially-relevant mass loading charged at fast charge rates. It is demonstrated that the local reaction progression and plating onset can not only be predicted accurately with a p2D numerical model, but that these processes follow a simple scaling law. Remarkably, the entire reaction histories of different electrodes charged at different rates (e.g., 160 μm thickness at 0.5C, 111 μm at 1C or 66 μm at 4C) were observed to have self-similar intercalation profiles. It is demonstrated that plating onset is in turn governed by the reaction profile which explains why both processes exhibit the same scaling behavior. Finally, operando measurements of local reaction dynamics are conducted for the first time in electrodes with channeled architectures, quantitatively determining how channels affect reaction uniformity and plating onset. Together, these results reveal underlying simplicity in the complex electrochemical environment of fast charging and lithium plating, improving understanding of this process. These fundamental insights are broadly applicable for design processes, modeling and experimental evaluation of lithium ion batteries.
This study presents a facile method to synthesize Type I Chevrel phases and utilizes X-ray absorption spectroscopy to reveal how intercalant identity can modify charge transfer and cluster anisotropy.
An optimized ether-based electrolyte is designed to suppress solvent co-intercalation and decomposition of graphite anodes, thereby enabling lithium–sulfur batteries with low N/P ratio.
A combined simulation and experimental study into mechanisms and effects of gas intercalation in ionic liquids confined to charged and neutral carbon nanotubes, providing insights for gas sensing and separation technologies.
Transition metal cation intercalation between the layers of two-dimensional (2D) metal halides is an underexplored research area. In this work we focus on the synthesis and physical property characterizations of two layered hybrid lead halides: a new compound [Cu(O 2 C–CH 2 –NH 2 ) 2 ]Pb 2 Br 4 and the previously reported [Cu(O 2 C–(CH 2 ) 3 –NH 3 ) 2 ]PbBr 4 . These compounds exhibit 2D layered crystal structures with incorporated Cu 2+ between the metal halide layers, which is achieved by combining Cu(II) and lead bromide with suitable amino acid precursors. The resultant [Cu(O 2 C–(CH 2 ) 3 –NH 3 ) 2 ]PbBr 4 adopts a 2D layered perovskite structure, whereas the new compound [Cu(O 2 C–CH 2 –NH 2 ) 2 ]Pb 2 Br 4 crystallizes with a new structure type based on edge-sharing dodecahedral PbBr5O3 building blocks. [Cu(O 2 C–CH 2 –NH 2 ) 2 ]Pb 2 Br 4 is a semiconductor with a bandgap of 3.25 eV. It shows anisotropic charge transport properties with a semiconductor resistivity of 1.44 × 10 10 Ω cm (measured along the a-axis) and 2.17 × 10 10 Ω cm (along the bc-plane), respectively. The fabricated prototype detector based on this material showed response to soft low-energy X-rays at 8 keV with a detector sensitivity of 1462.7 μCGy –1 cm –2 , indicating its potential application for ionizing radiation detection. Finally, these encouraging results are discussed together with the results from density functional theory calculations, optical, magnetic, and thermal property characterization experiments.
Nanocomposites of cobalt ferrite (CFO) magnetic nanoparticles intercalated on carbon nanotubes (CNTs) are evaluated as a nanomagnetic ultrasensitive sensor for the environmental toxin, hexavalent chromium (Cr-VI). Specifically, the structural and magnetic changes that accompany the infiltration of the CFO/CNTs by Cr-VI are presented. Extended x-ray absorption fine structure (EXAFS) shows that the atomic spacing within the CFO structure changes in the presence of Cr, suggesting that the Cr is incorporated into the nanoparticles. Vibrating sample magnetometry (VSM) reveals that CFO/CNTs composite infiltrated with Cr-VI have a 71% enhancement in saturation magnetization compared with the uninfiltrated CFO/CNTs, while small-angle neutron scattering (SANS) suggests that this magnetic enhancement is not associated with the nanoparticle lengthscales, but may arise from longer-ranged clusters. Both VSM and SANS clearly demonstrate that the Cr-doped CFO/CNTs are hysteretic with a net magnetization at remanence that is about 1/3 that of saturation, while this hysteresis is absent in the undoped CFO/CNTs. These magnetic differences at either remanence or saturation are promising for the magnetic detection of Cr-VI using CFO/CNTs sensors.
Electrical double-layer capacitors (EDLCs) are of increasing importance in energy storage from renewable sources. The properties of the electrode and electrolyte materials influence the energy and power densities of EDLCs. We examined the specific capacitance and ion dynamics of a protic ionic liquid confined in pre-intercalated Ti 3 C 2 T x MXene. Our electrochemical measurements demonstrated that the creation of a protic ionic liquid, 1-butyl-3-H-imidazolium bis(trifluoromethanesulfonyl)imide (BuIMH-NTf2), using a mixture of ionic liquid, 1-butyl imidazole (BuIM), and salt, bis(trifluoromethanesulfonyl)imide (HNTf2), in a ratio of 0.8:0.2 led to the optimal capacitance. Remarkably, quasi-elastic neutron scattering measurements revealed increased particle mobility at this composition, attributed to the more efficient accumulation of BuIMH + on the electrode surface. This deposit of additional ions results in fewer BuIM molecules away from the surface, enhancing their mobility due to reduced crowding. This composition-dependent electrochemical behavior will guide the formulation of more efficient protic ionic liquid systems, enabling faster ion transport in energy storage devices.
Experimental studies indicate that 3D crystalline metal nanoclusters (NCs) intercalated under the surface of graphite have flat-topped equilibrated shapes. In this work, we characterize the shapes of these facetted NCs sandwiched between a blanketing graphene layer and the underlying graphite substrate. Specifically, we focus on the cases of fcc Cu and hcp Fe NCs. Furthermore, the analysis involves numerical minimization of the system energy for a specified NC volume and NC height, the latter corresponding to the separation between parallel top and bottom facets. Our numerical analysis quantifies how the distance of the side facet planes from center of the nanocluster varies linearly with a natural characteristic linear dimension of the nanocluster. Calculated shapes of fcc Cu and hcp Fe NCs are consistent with the hexagonal footprints observed in scanning tunneling microscopy studies.
Here, we present results of atomic-force-microscopy-based friction measurements on Re-doped molybdenum disulfide (MoS 2 ). In stark contrast to the widespread observation of decreasing friction with increasing number of layers on two-dimensional (2D) materials, friction on Re-doped MoS 2 exhibits an anomalous, i.e. inverse, dependence on the number of layers. Raman spectroscopy measurements combined with ab initio calculations reveal signatures of Re intercalation. Calculations suggest an increase in out-of-plane stiffness that inversely correlates with the number of layers as the physical mechanism behind this remarkable observation, revealing a distinctive regime of puckering for 2D materials.
Density functional theory based calculations and experimental analysis on a limited number of real samples are performed to study how the presence of silver intercalated in the van der Waals gap of few-layer MoS 2 affects the low-frequency Raman active modes of this material. Silver is found to predominantly affect the breathing-like and shear-like vibrational modes of MoS 2 . These modes correspond to quasi-rigid movements of each individual layer with a restoring force (and, in turn, frequency) that is determined by modulations in the weak interlayer interactions. Noticeable red-shifts with increasing Ag concentration are found for all low-frequency modes. This finding indicates the potential for low-frequency vibrations as useful gauges for practical determination of silver concentration using low-frequency Raman spectroscopy. Finally, this work also describes a semi-classical linear chain model that allows to extrapolate results to a large number of layers. Further, first-principles calculations show how Raman spectroscopy can be used to characterize the quality of the two-dimensional interface between MoS 2 and a silver substrate.
While exploring potential superconductors in the C-S-H ternary system using first-principles crystal structure prediction methods, we uncovered a class of hydride perovskites based on the intercalation of methane into an H 3 S framework. These intriguing H 3 S–CH 4 structures emerge as metastable at ~100 GPa. Further, electron-phonon coupling calculations indicate that phases with CSH 7 stoichiometry are potential superconductors with $T_c$ values ranging from 100 K to 190 K at megabar pressures. The results are expected to guide the experimental search for new high-$T_c$ superconductors, including those stable at lower pressures than previously documented superconducting hydrides such as H 3 S and LaH 10 .
Recently there has been intense interest in kagome metals, which are expected to host flat bands (FBs). However, the observed “FBs” are not flat over the whole two-dimensional Brillouin zone and overlap strongly with other bands. In fact, the FB does not truly exist in a default d-orbital kagome lattice, and the conditions for its existence in kagome metals are unknown. Here, based on tight-binding model analyses of the interplay between orbital and lattice symmetry, we establish such conditions. Additionally, we show that for a single d-orbital kagome lattice assuming large crystal field splitting (CFS), only the d z 2 orbital gives rise to a FB, while d xy , d x 2 -y 2 , d xz , and d yz orbitals can only produce a FB with a rotated d-orbital basis so that they conform with the underlying kagome lattice symmetry. Most importantly, we demonstrate that both conditions of d-orbital rotation and large CFS can be ideally satisfied by intercalating the kagome lattice with a hexagonal sublattice without disrupting the destructive interference of FB wave function. Furthermore, we propose layered metalorganic frameworks as promising candidate kagome metals to realize FBs.
Although doping with alkali atoms is a powerful technique for introducing charge carriers into physical systems, the resulting charge-transfer systems are generally not air stable. Here, in this paper, we describe computationally a strategy towards increasing the stability of alkali-doped materials that employs stoichiometrically unbalanced salt crystals with excess cations (which could be deposited during, e.g., in situ gating) to achieve doping levels similar to those attained by pure alkali metal doping. The crystalline interior of the salt crystal acts as a template to stabilize the excess dopant atoms against oxidation and deintercalation, which otherwise would be highly favorable. We characterize this doping method for graphene, NbSe 2 , and Bi 2 Se 3 and its effect on direct-to-indirect band gap transitions, 2D superconductivity, and thermoelectric performance. Salt intercalation should be generally applicable to systems which can accommodate this “ionic crystal” doping (and particularly favorable when geometrical packing constraints favor nonstoichiometry).
We introduce global connectivity, Ω, which quantifies the detailed connectivity of a material and accurately captures reactivity behavior. Here, we demonstrate that combining global and local connectivity describes how metal oxides interact with hydrogen. Blending density functional theory, graph theory, and machine learning we built a reactivity model which accurately predicts hydrogen intercalation potentials of different metal oxides experimentally measured in the lab. The use of global connectivity can accelerate materials design through the development of novel structure-property relationships.
We image local superfluid density in single crystals of Pd-intercalated ErTe 3 below the superconducting critical temperature T c , well below the onset temperature T CDW of (disordered) charge-density-wave order. We find no detectable inhomogeneities on micron scales. Furthermore, we observe a rapid increase of the superfluid density below T c , deviating from the behavior expected in a conventional Bardeen-Cooper-Schrieffer superconductor, and show that the temperature dependence is qualitatively consistent with a combination of quantum and thermal phase fluctuations.
Despite extensive research on oxide battery cathodes that transcend classical cationic redox activity, the detailed interplay between structural transformations and electronic redox processes remains insufficiently understood. We report a detailed study of the sequential structural and electronic changes in Li 2 RuO 3 upon lithium intercalation, characterized by powder x-ray and neutron diffraction alongside Ru and O K-edge x-ray absorption spectroscopy (XAS), and guided by operando synchrotron x-ray diffraction. During delithiation, Li 2 RuO 3 evolves from a well-defined monoclinic state to a complex trigonal phase via multiple intermediate structures, marked by significant changes in Ru-O bond distances that closely track the transition from a classical cationic redox to an unconventional process centered at oxygen states. Armed with high-quality atomic structural descriptions, computational models of the O K-edge XAS closely reproduce the experimentally observed spectral shifts. Lastly, we relate observations of electrochemical hysteresis with concurrent changes in the pathways of structural and electronic transitions. In conclusion, our results not only clarify the mechanisms underpinning voltage hysteresis in a model for lattice oxygen redox but also underscore the importance of structural fidelity in modeling redox behavior when this type of complex reactivity is present.
Abstract The availability of water and the type of interlayer anions present affect the arrangement and interlayer spacing of layered double hydroxide (LDH). A systematic study of the effect of relative humidity (RH) on the basal spacing of phosphate intercalated, magnesium aluminum LDHs (MgAl–PO 4 LDH) was conducted, confirming that MgAl‐PO 4 LDH exhibit distinct interlayer spacing corresponding to separate low‐ and high‐hydration states produced when exposed to low and high humidity conditions. The transition from the low‐ to high‐hydration form begins when RH exceeds 33% and is accompanied by the transition from one to two interlayers of water. An improved understanding of the effect of RH on MgAl–PO 4 LDHs will enable more accurate atomistic modeling and experimental characterization of MgAl–PO 4 LDHs and may lead to improvements in the tunability of MgAl‐PO 4 LDHs for commercial applications such as slow‐release fertilizer.