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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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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Electrochemical Li Intercalation in Black Phosphorus: In Situ and Ex Situ Studies

A systematic study on electrochemical charge transfer in Li-doped black phosphorous (BP) was carried out by both in-situ and ex-situ Raman scattering. Galvanostatic discharge of dedicated in-situ electrochemical cell for Raman spectroscopy was used to study time evolution of vibrational modes under lithiation. In addition to the peak broadening which is a result of structural expansion, peaks corresponding to all three atomic vibrational modes A 1 g , B 2 g and A 2 g were found to red-shift as a result of lithiation. Peaks B 2 g and A 2 g were shifted about 1.6 times more towards lower wavenumbers in comparison to A 1 g . Further characterizations using optical and electron microscopy showed that the intercalation of BP is highly anisotropic, where channels along the zigzag direction were found to be the easy direction for intercalation. X-ray diffraction on intercalated samples confirmed a reduction of thickness as lithiation weakens interlayer bonding, thus resulting in a partial exfoliation of BP flakes. Here, first principle studies using density function theory (DFT) were used to develop a theoretical model for the intercalation mechanism. The discrepancy between the experimental and the theoretical results was also addressed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Nanoscale hydration in layered manganese oxides

Birnessite is a layered MnO2 mineral with a nanoscale interlayer region that accommodates layers of intercalated water. Variable distributions of Mn sites with oxidation states of II, III and IV are responsible for the high catalytic reactivity of birnessite in nature and as a valuable candidate for energy storage solutions. We here report water loading capabilities and the vibrational spectral signatures of two forms of birnessite of strongly contrasting particle size. Using X-ray diffraction we find that potassium-birnessite accommodates no more than one monolayer (1W) of water in its interlayer region. Molecular simulations show that this is an energetically favorable hydration state where interlayer potassium-water and direct water-birnessite interactions are greater than at other hydration levels. Simulations also suggest a stable 2W state but that is not achieved experimentally by contact with water vapor. Finally, this work provides a means to predict the distribution of adsorbed and interlayer water molecules using a recently developed composite model.

Cheng, Wei↗
DOE OSTI2020

Electronic Structure of Double-Layer Epitaxial Graphene on SiC(0001) Modified by Gd Intercalation

In this work, we systematically study the effects of Gd adsorption and intercalation on the electronic band structure of double-layer epitaxial graphene on Si-terminated SiC(0001) by first-principles calculations. We show that Gd adsorption and intercalation exhibit strong effects on the coupling between the graphene layers and between the buffer layer and substrate. Different adsorption/intercalation geometries can result in very different electron band structures. The number of Dirac cones and the positions of the Dirac cones relative to the Fermi level can be effectively manipulated through controlling the Gd adsorption/intercalation geometries. Our calculations provide useful insights to guide the experimental design of graphene-based materials with desirable functionalities for applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Access to Ru(IV)–Ru(V) and Ru(V)–Ru(VI) Redox in Layered Li 7 RuO 6 via Intercalation Reactions

The push to increase the capacity of oxides to store charge as Li-ion battery cathodes has challenged our knowledge of the boundaries of redox chemistry and its relationship to the atomic structure. Layered phases with Ru are now classical models in the quest for refined theories. Current understanding dictates that the highest formal state that can be reached in them is Ru(V), after which activity centered at the oxide anions is triggered. Yet, this picture is challenged by this investigation of the intercalation chemistry of Li 7 RuO 6 . Coupling structural and spectroscopic analysis with computational simulations, we show that Li 7 RuO 6 is capable of highly reversible lithiation to Li 8 RuO 6 through the Ru(V)/Ru(IV) redox couple. Further, Li 7 RuO 6 can also undergo anodic Li deintercalation, showing clear evidence of the reversible formation of Ru(VI) with octahedral coordination, an unusual state that is not accessible in other layered oxides. The results highlight the versatility of the Ru-O bond to undergo distinct redox transitions depending on the specific layered arrangements. They enrich our understanding of redox chemistry in solids while underscoring the need for descriptions of charge compensation that reflect the nuance of covalent interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Cesium intercalation of graphene: A 2D protective layer on alkali antimonide photocathode

Alkali antimonide photocathodes have wide applications in free-electron lasers and electron cooling. The short lifetime of alkali antimonide photocathodes necessitates frequent replacement of the photocathodes during a beam operation. Furthermore, exposure to mediocre vacuum causes loss of photocathode quantum efficiency due to the chemical reaction with residual gas molecules. Theoretical analyses have shown that covering an alkali antimonide photocathode with a monolayer graphene or hexagonal boron nitride protects it in a coarse vacuum environment due to the inhibition of chemical reactions with residual gas molecules. Alkali antimonide photocathodes require an ultra-high vacuum environment, and depositing a monolayer 2D material on it poses a serious challenge. In the present work, we have incorporated a novel method known as intercalation, in which alkali atoms pass through the defects of a graphene thin film to create a photocathode material underneath. Initially, Sb was deposited on a Si substrate, and a monolayer graphene was transferred on top of the Sb film. Heat cleaning around 550–600 °C effectively removed the Sb oxides, leaving metallic Sb underneath the graphene layer. Depositing Cs on top of a monolayer graphene enabled the intercalation process. Atomic force microscopy, Raman spectroscopy, x-ray photoelectron spectroscopy, low energy electron microscopy, and x-ray diffraction measurements were performed to evaluate photocathode formation underneath the monolayer graphene. Our analysis shows that Cs penetrated the graphene and reacted with Sb and formed Cs 3 Sb.

2D materials↗
DOE OSTI2021

Layered Transition Metal Oxides as Ca Intercalation Cathodes: A Systematic First-Principles Evaluation

Finding high-voltage Ca cathode materials is a critical step to unleashing the full potential of high-energy-density Ca-ion batteries. Therefore, first-principles calculations are used to demonstrate that P-type layered calcium transition metal (TM) oxide materials (CaTM 2 O 4 ) with a range of TM substitutions (TM = Ti, V, Cr, Mn, Fe, Co, and Ni) have excellent battery-related properties including thermodynamic stability, average voltage, energy density, synthesizability, ionic mobility, and electronic structure. However, the thermodynamic stability of the charged phase and TM redox activity are shown to be sensitive to TM selection, with CaCo 2 O 4 having the best balance of all considered properties. The utility of combining multiple TMs to expand the chemical search space for TM substitutions is demonstrated by mixing Co and Ni in layered CaTM 2 O 4 .

25 ENERGY STORAGE↗
DOE OSTI2026

Emergent ferromagnetism and unusual irreversible magnetoresistance in an intercalated van der Waals antiferromagnet

Orthorhombic air-stable two-dimensional (2D) antiferromagnet (AFM) CrSBr has attracted much research interest lately thanks to its rich magnetic behaviors together with its remarkable electronic, excitonic, and polaritonic properties. Here, we report a reliable electrochemical intercalation method by inserting large tetrabutylammonium (TBA + ) ions into CrSBr layers. Magnetically, such intercalation efficiently suppresses the interlayer AFM and induces a ferromagnetic (FM) order with a much-enhanced transition temperature up to 200 K, nearly 70 K higher than the AFM onset of 132 K in pristine CrSBr. Electronically, the TBA + intercalation not only increases the electric conductivity of CrSBr, which is further enhanced by magnetic fields, but also introduces a giant negative irreversible magnetoresistance. This work demonstrates the tunable magnetic and electronic properties of CrSBr as well as their interplay, paving the way for advanced spintronic and magnetic memory devices.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Visualizing the out-of-plane electronic dispersions in an intercalated transition metal dichalcogenide

Layered transition metal dichalcogenides have a rich phase diagram and they feature two-dimensionality in numerous physical properties. Co 1/3 NbS 2 is one of the newest members of this family where Co atoms are intercalated into the van der Waals gaps between NbS 2 layers. Here, we study the three-dimensional electronic band structure of Co 1/3 NbS 2 using both surface and bulk sensitive angle-resolved photoemission spectroscopy. We show that the electronic bands do not fit into the rigid band shift picture after the Co intercalation. Instead, Co 1/3 NbS 2 displays a different orbital character near the Fermi level compared to the pristine NbS 2 compound and has a clear band dispersion in the k z direction despite its layered structure. Our photoemission study demonstrates the out-of-plane electronic correlations introduced by the Co intercalation, thus offering a different perspective on this compound. Finally, we propose how Fermi level tuning could lead to exotic phases such as spin density wave instability.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Intercalation of Mg into a Few-Layer Phyllomanganate in Non-aqueous Electrolytes at Room Temperature

The use of oxide cathodes in Mg batteries would unlock a potential energy storage system that delivers high-energy density. However, poor kinetics of Mg diffusion in known solid oxide lattices strongly limits reversible intercalation, which motivates the sustained exploration of new candidates. Herein, nanocrystals of a few-layer phyllomanganate, reminiscent of the mineral vernadite, were shown to have considerable electrochemical activity toward Mg intercalation at room temperature, where it delivered similar to 190 mAh g- 1 at similar to 1.9 V (vs Mg/Mg 2+ ) in batteries paired with a Mg metal anode. Multimodal characterization confirmed the notable degree of reversible intercalation by probing the structural, compositional, and redox changes undertaken by the oxide. Distinct levels of Mg activity were also observed while varying the content of small amounts of lattice water and the temperature of the reaction. The results reaffirm the prospects for operational Mg batteries using oxide cathode in moderate conditions, overcoming current limits of performance of this prospective technology.

25 ENERGY STORAGE↗
DOE OSTI2020

Spontaneous self-intercalation of copper atoms into transition metal dichalcogenides

Intercalated transition metal dichalcogenides (TMDs) have attracted substantial interest due to their exciting electronic properties. Here, we report a unique approach where copper (Cu) atoms from bulk Cu solid intercalate spontaneously into van der Waals (vdW) gaps of group IV and V layered TMDs at room temperature and atmospheric pressure. This distinctive phenomenon is used to develop a strategy to synthesize Cu species–intercalated layered TMD compounds. A series of Cu-intercalated 2H-NbS 2 compounds were obtained with homogeneous distribution of Cu intercalates in the form of monovalent Cu (I), occupying the tetrahedral sites coordinated by S atoms within the interlayer space of NbS 2 . The Fermi level of NbS 2 shifts up because of the intercalation of Cu, resulting in the improvement of electrical conductivity in the z-direction. On the other hand, intercalation of Cu into vdW gaps of NbS 2 systematically suppresses the superconducting transition temperature (T c ) and superconducting volume fraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Phase Discovery and Selected Synthesis of Subvalent Niobium Tellurides Using a Polytelluride Flux Strategy

Transition metal subchalcogenides involve electron-rich metals and can facilitate an in-depth understanding of the relationships among quantum properties such as superconductivity, charge density wave, and topological band structures. However, effective experimental routes toward synthesizing transition metal subchalcogenides are still lacking, hindering the development of new quantum materials. Herein, we propose a eutectic polytelluride flux strategy as an excellent solution to address phase discovery and crystal growth in transition metal subtelluride systems. We report new phases easily and selectively synthesized using a eutectic “K 3 Te 4 ” polytelluride flux upon adjusting the ratio of Nb metal to flux in the starting materials (K/Nb/Te = 3:x:4). Using a high Nb content in the solvent (x = 2 and 1), crystals of KNb 3 Te 3 O 0.38 and K 0.9 Nb 3 Te 4 are obtained. Both subtellurides exhibit diverse Nb clusters, including face-sharing and edge-sharing Nb 6 octahedral columns and zig-zag Nb chains. Reducing the Nb content to x = 0.33 leads to the formation of a layered compound, K 1.06 NbTe 2 . This compound comprises a NbTe 6 trigonal prism with K intercalated between the layers. Single crystals of known binary Nb tellurides can also be grown using another eutectic flux “KTe 3 . 2 ”, and the obtained NbTe 2 exhibits a new polymorphism with extra trimerization along the b-axis in the Nb–Nb bonded double zig-zag cluster. Finally, precise control over the structural dimensionality and oxidation state, combined with the facile crystal growth process, makes our synthetic strategy an efficient route to explore quantum materials in transition metal subchalcogenides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Operando Interaction and Transformation of Metastable Defects in Layered Oxides for Na‐Ion Batteries

Non-equilibrium defects often dictate the macroscopic properties of materials. They largely define the reversibility and kinetics of processes in intercalation hosts in rechargeable batteries. Recently, imaging methods have demonstrated that transient dislocations briefly appear in intercalation hosts during ion diffusion. Despite new discoveries, the understanding of impact, formation and self-healing mechanisms of transient defects, including and beyond dislocations, is lacking. Here, operando X-ray Bragg Coherent Diffractive Imaging (BCDI) and diffraction peak analysis capture the stages of formation of a unique metastable domain boundary, defect self-healing, and resolve the local impact of defects on ionic diffusion in Na x Ni 1-y MnyO 2 intercalation hosts in a charging sodium-ion battery. Results, applicable to a wide range of layered intercalation materials due to the shared nature of framework layers, elucidate new dynamics of transient defects and their connection to macroscopic properties, and suggest how to control the nanostructure dynamics.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Electrochemical Control of the Ultrafast Lattice Response of a Layered Semimetal

The unique layer-stacking in two-dimensional (2D) van der Waals materials facilitates the formation of nearly degenerate phases of matter and opens novel routes for the design of low-power, reconfigurable functional materials. Electrochemical ion intercalation between stacked layers offers a promising approach to stabilize bulk metastable phases and to explore the effects of extreme carrier doping and strain. However, in situ characterization methods to study the structural evolution and dynamical functional properties of these intercalated materials remains limited. Here a novel experimental platform is presented capable of simultaneously performing electrochemical lithium-ion intercalation and multimodal ultrafast characterization of the lattice using both electron diffraction and nonlinear optical techniques. Using the layered semimetal WTe 2 as a model system, the interlayer shear phonon mode that modulates stacking between 2Dlayers is probed, showing that small amounts of lithiation enhance the amplitude and lifetime of the phonon, contrary to expectations. This results from the dynamically fluctuating and anharmonic structure between nearly degenerate phases at room temperature, which can be stabilized by electronic carriers accompanying the inserted lithium ions. At high lithiation, the T d ’ structure emerges and quenches the phonon response. This work defines new approaches for using electrochemistry to engineer the dynamic structure of 2D materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

In Situ Visualization of Local Distortions in the High- T c Molecule-Intercalated Li x (C 5 H 5 N) y Fe 2– z Se 2 Superconductor

A time-resolved synchrotron X-ray total scattering study sheds light on the evolution of the different structural length scales involved during the intercalation of the layered iron–selenide host by organic molecular donors, aiming at the formation of the expanded-lattice Li x (C 5 H 5 N) y Fe 2– z Se 2 hybrid superconductor. The intercalates are found to crystallize in the tetragonal ThCr 2 Si 2 -type structure at the average level, however, with an enhanced interlayer iron–selenide spacing ( d = 16.2 Å) that accommodates the heterocyclic molecular spacers. Quantitative atomic pair distribution function (PDF) analysis at variable times suggests distorted FeSe 4 tetrahedral local environments that appear swollen with respect to those in the parent β-FeSe. Simultaneously acquired in situ synchrotron X-ray powder diffraction data disclose that secondary phases (α-Fe and Li 2 Se) grow significantly when a higher lithium concentration is used in the solvothermal reaction or when the solution is aged. These observations are in line with the strongly reducing character of the intercalation medium’s solvated electrons that mediate the defect chemistry of the expanded-lattice superconductor. In the latter, intralayer correlated local distortions indicate electron-donating aspects that reflect in somewhat enlarged Fe–Se bonds. Additionally, they also reveal a degree of relief of chemical pressure associated with a large distance between Fe and Se sheets (“taller” anion height) and a stretched Fe–Fe square planar topology. The elongation of the latter, derived from the in situ PDF study, speaks for a plausible increase in the Fe-site vacancy concentration. The evolution of the local structural parameters suggests an optimum reaction window where kinetically stabilized phases resemble the distortions of the edge-sharing Fe–Se tetrahedra, required for a high- T c in expanded-lattice iron-chalcogenides.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Microstructure‐Dependent Sodium Storage Mechanisms in Hard Carbon Anodes

Sustainable energy storage is essential to support the transition to renewables and meet the increasing demand for energy. Sodium‐ion batteries (NIBs) are attractive for grid‐scale energy storage due to the abundance and low cost of sodium, sustainability of other battery components, and electrochemical performance. Hard carbon (HC) is a leading anode material for NIBs, but its complex microstructure complicates the understanding of sodium storage mechanisms. Using X‐ray total scattering and density functional theory calculations, this study clarifies how HC's microstructural variations influence sodium storage across the slope (high potential) and plateau (low potential) regions of the potential capacity curve. In the slope region, sodium initially adsorbs at high‐binding energy defect sites and subsequently intercalates between graphene layers, adsorbing at low‐binding energy defect sites, correlating with different slopes observed during initial sodiation. Initial irreversibility arises from sodium trapping at surface defects and solid electrolyte interface formation. In the plateau region, sodium simultaneously intercalates and fills pores, influenced by pore size, interlayer spacing, and defect concentration. HCs with larger pore sizes form larger sodium clusters. In conclusion, the proposed mechanism underscores the role of microstructure engineering in enhancing HC performance and advancing NIBs for grid‐scale energy storage.

36 MATERIALS SCIENCE↗