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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 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Zero-field Hall effect emerging from a non-Fermi liquid in a collinear antiferromagnet V 1/3 NbS 2

Magnetically intercalated transition metal dichalcogenides (TMDs) provide a versatile three-dimensional (3D) material platform to explore quantum phenomena and functionalities that emerge from an intricate interplay among magnetism, band structure, and electronic correlations. Here, we report the observation of a nearly magnetization-free anomalous Hall effect (AHE) accompanied by non-Fermi liquid (NFL) behavior and collinear antiferromagnetism (AFM) in V 1/3 NbS 2 . Our single-crystal neutron diffraction measurements identify a commensurate, collinear AFM order formed by intercalated V moments. In the magnetically ordered state, the spontaneous AHE is tenfold greater than expected from empirical scaling with magnetization, and this strongly enhanced AHE arises in the NFL regime that violates the quasiparticle picture. V 1/3 NbS 2 challenges the existing single-particle framework for understanding AHEs based on one-body Berry curvature and highlights the potential of magnetically intercalated TMDs to unveil new electronic functionalities where many-body correlations play a critical role.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Phase evolution and structural modulation during in situ lithiation of MoS 2 , WS 2 and graphite in TEM

Li-ion batteries function by Li intercalating into and through the layered electrode materials. Intercalation is a solid-state interaction resulting in the formation of new phases. The new observations presented here reveal that at the nanoscale the intercalation mechanism is fundamentally different from the existing models and is actually driven by nonuniform phase distributions rather than the localized Li concentration: the lithiation process is a ‘distribution-dependent’ phenomena. Direct structure imaging of 2H and 1T dual-phase microstructures in lithiated MoS 2 and WS 2 along with the localized chemical segregation has been demonstrated in the current study. Li, a perennial challenge for the TEM, is detected and imaged using a low-dose, direct-electron detection camera on an aberration-corrected TEM and confirmed by image simulation. This study shows the presence of fully lithiated nanoscale domains of 2D host matrix in the vicinity of Li-lean regions. This confirms the nanoscale phase formation followed by Oswald ripening, where the less-stable smaller domains dissolves at the expense of the larger and more stable phases.

25 ENERGY STORAGE↗
DOE OSTI2020

Pursuing graphite-based K-ion O 2 batteries: a lesson from Li-ion batteries

The replacement of lithium metal by lithium intercalated graphite was crucial for developing safe lithium-ion batteries. Superoxide-based potassium–oxygen batteries represent an exciting metal–oxygen battery with the highest energy efficiencies. However, using potassium metal is a more serious safety threat than lithium. Herein, we explore the possibility of graphite-intercalation anodes for potassium-ion oxygen batteries (PIOBs) with enhanced safety. This work demonstrates for the first time that establishing an artificial potassium salt-rich solid electrolyte interphase (SEI) enables a reversible graphite-intercalation anode (249.6 mA h g -1 after 600 cycles) in a potassium bis(trifluoromethanesulfonyl)imide (KTFSI)-based localized high-concentration electrolyte. Such an electrolyte is stable with the superoxide cathode. The PIOB delivers energy efficiencies above 90% at a depth of discharge (DOD) of 25% for 80 cycles. A three-electrode measurement shows that its overpotential mainly comes from the anode. The lifespan is limited to the gradual degradation of the artificial SEI caused by oxygen crossover. This work represents a step towards achieving holistic anode–electrolyte–cathode compatibility in a PIOB and its realistic evaluation under a controlled DOD.

25 ENERGY STORAGE↗
DOE OSTI2022

X-ray absorption spectroscopy insights on the structure anisotropy and charge transfer in Chevrel Phase chalcogenides

Here, the electronic structure and local coordination of binary (Mo 6 T 8 ) and ternary Chevrel Phases (M x Mo 6 T 8 ) are investigated for a range of metal intercalant and chalcogen compositions. We evaluate differences in the Mo L 3 -edge and K-edge X-ray absorption near edge structure across the suite of chalcogenides M x Mo 6 T 8 (M = Cu, Ni, x = 1–2, T = S, Se, Te), quantifying the effect of compositional and structural modification on electronic structure. Furthermore, we highlight the expansion, contraction, and anisotropy of Mo 6 clusters within these Chevrel Phase frameworks through extended X-ray absorption fine structure analysis. Our results show that metal-to-cluster charge transfer upon intercalation is dominated by the chalcogen acceptors, evidenced by significant changes in their respective X-ray absorption spectra in comparison to relatively unaffected Mo cations. These results explain the effects of metal intercalation on the electronic and local structure of Chevrel Phases across various chalcogen compositions, and aid in rationalizing electron distribution within the structure.

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

Feasibility study of Mg storage in a bilayer silicene anode via application of an external electric field

With the goal of developing a Si-based anode for Mg-ion batteries (MIBs) that is both efficient and compatible with the current semiconductor industry, the current research utilized classical Molecular Dynamics (MD) simulation in investigating the intercalation of a Mg 2+ ion under an external electric field (E-field) in a 2D bilayer silicene anode (BSA). First principles density functional theory calculations were used to validate the implemented EDIP potentials. Our simulation shows that there exists an optimum E-field value in the range of 0.2–0.4 V Å –1 for Mg 2+ intercalation in BSA. To study the effect of the E-field on Mg 2+ ions, an exhaustive spread of investigations was carried out under different boundary conditions, including calculations of mean square displacement (MSD), interaction energy, radial distribution function (RDF), and trajectory of ions. Our results show that the Mg 2+ ions form a stable bond with Si in BSA. The effects of E-field direction and operating temperature were also investigated. In the X–Y plane in the 0°–45° range, 15° from the X-direction was found to be the optimum direction for intercalation. The results of this work also suggest that BSA does not undergo drastic structural changes during the charging cycles with the highest operating temperature being ~300 K

25 ENERGY STORAGE↗
DOE OSTI2024

A high-throughput and data-driven computational framework for novel quantum materials

Two-dimensional layered materials, such as transition metal dichalcogenides (TMDs), possess an intrinsic van der Waals gap at the layer interface, allowing for remarkable tunability of the optoelectronic features via external intercalation of foreign guests such as atoms, ions, or molecules. Herein, we introduce a high-throughput, data-driven computational framework for the design of novel quantum materials derived from intercalating planar conjugated organic molecules into bilayer transition metal dichalcogenides and dioxides. By combining first-principles methods, material informatics, and machine learning, we characterize the energetic and mechanical stability of this new class of materials and identify the fifty (50) most stable hybrid materials from a vast configurational space comprising ∼105 materials, employing intercalation energy as the screening criterion.

Kastuar, Srihari M. (ORCID:0000000279001561)↗
DOE OSTI2022

Copper migration and surface oxidation of CuxBi2Se3 in ambient pressure environments

Abstract Chemical modifications such as intercalation can be used to modify surface properties or to further functionalize the surface states of topological insulators (TIs). Using ambient pressure x-ray photoelectron spectroscopy, we report copper migration in C u x B i 2 S e 3 , which occurs on a timescale of hours to days after initial surface cleaving. The increase in near-surface copper proceeds along with the oxidation of the sample surface and large changes in the selenium content. These complex changes are further modeled with core-level spectroscopy simulations, which suggest a composition gradient near the surface which develops with oxygen exposure. Our results shed light on a new phenomenon that must be considered for intercalated TIs—and intercalated materials in general—that surface chemical composition can change when specimens are exposed to ambient conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Developing Novel Electrode Materials for Aqueous Battery

Aqueous rechargeable batteries (ARBs) are particularly interesting for large-scale energy storage due to their inherent safety, superior rate capability and environmental friendliness. However, ARBs are not widely explored as yet, so we proposed designing, preparing, and testing new intercalation materials for ARBs. Development of these electrodes will enrich the electrode chemistry of existing ARBs, open up new avenues for high-performance electrode and system design, offer opportunities to improve energy efficiency of water purification, and inform future development of controls strategies and management systems for stationary aqueous energy storage. Researchers from Bosch and LBNL collaborated on relevant materials to pursue and the general design of experiments to implement. Bosch researchers prepared and fabricated the electrodes and used various characterization facilities at LBNL to evaluate electrode performance in-device. The research collaboration resulted in identifying electrode materials capable of Na + and Ca 2+ intercalation in aqueous systems, and their application for desalination was explored using testing platform available at LBNL. Besides the specific materials and their performance, the data collected during the study was also used to inform a broader techno-economic analysis to compare intercalation-desalination technique to commercially available capacitive desalination approach. Outcomes of this research effort will be published in peer-reviewed journals.

25 ENERGY STORAGE↗
DOE OSTI2021

Layer spacing gradient (NaLi) 1–x CoO 2 for electrochemical Li extraction

Designing materials with high Li to Na selectivity is the key for direct extraction of Li from unconventional sources, such as seawater, without complex separations. However, material discovery is hindered by an insufficient understanding on how a material's composition and structure relate to Li selectivity during electrochemical co-intercalation. Here, we synthesized a core-shell structured (NaLi) 1-x CoO 2 with a core Li phase (Li 0.94 CoO 2 ), a shell Na phase (Na 0.51 CoO 2 ), and a transition intermediate phase via Na ion-exchange of parent Li 1-x CoO 2 . We reveal that the chemical compositions and spatial relation of these phases play critical roles in governing high Li to Na selectivity. The core Li phase restricts large layer spacing expansion and inhibits Na intercalation. The shell Na phase serves to maintain the electrode stability against further Na ion exchange. With the layer spacing gradient design, we achieved a high Li selectivity of 1.5 x 10 5 with a recovery of similar to 7.6:1 Li to Na from 1:20,000 initial ratio.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Multifunctional Utilization of Pitch-Coated Carbon Fibers in Lithium-Based Rechargeable Batteries

This work reports carbon fibers as an electrode material and current collector for dual-carbon and lithium-ion batteries. Here, fully graphitic and semigraphitic carbon fibers undergo anion intercalation beyond 4.5 V versus Li/Li + . Symmetric dual-carbon full cells using a pitch-coated fully graphitic carbon fiber mat as both cathode and anode delivers an energy-density of 276 and 322 Wh kg -1 at 342 W kg -1 power density in the voltage range of 3.0–5.0 and 3.0–5.2 V, respectively. On the other hand, nongraphitic carbon fibers do not exhibit anion intercalation up to 5.2 V and can be used as a current collector. They also possess a larger number of Li + storage sites in their randomly oriented microstructure when used as an anode. A lithium-ion full cell with double carbon-coated C-LiFePO 4 loaded on nongraphitic carbon fiber as a cathode and pitch-coated nongraphitic carbon fiber as an anode exhibits 202.6 and 75.2 Wh kg -1 energy density at power densities of 46.75 W kg -1 and 11.7 kW kg -1 , respectively in 2.0–3.5 V range. This pitch-coated carbon fiber-based battery configuration eliminates the need for metal foils and costly fluorinated binders, lowers overall weight of the cell, and is capable of sustaining mechanical stress and thermal shock.

PF6− intercalation↗
DOE OSTI2022

Amorphization of Pseudocapacitive T−Nb 2 O 5 Accelerates Lithium Diffusivity as Revealed Using Tunable Isomorphic Architectures

Abstract Intercalation pseudocapacitance can combine capacitor‐like power densities with battery‐like energy densities. Such surface‐limited behavior requires rapid diffusion where amorphization can increase solid‐state diffusivity. Here intercalation pseudocapacitive materials with tailored extents of amorphization in T‐Nb 2 O 5 are first reported. Amorphization was characterized with WAXS, XPS, XAFS, and EPR which suggested a peroxide‐rich (O 2 2− ) surface that was consistent with DFT predictions. A series of tunable isomorphic architectures enabled comparisons while independently varying transport parameters. Through process of elimination, solid‐state lithium diffusion was identified as the dominant diffusive‐constraint dictating the maximum voltage sweep rate for surface‐limited kinetics ( v SLT ), termed the Surface‐Limited Threshold (SLT). The v SLT increased with amorphization however stable cycling required crystalline T‐Nb 2 O 5 . A current‐response model using series‐impedances well‐matched these observations. This perspective revealed that amorphization of T‐Nb 2 O 5 enhanced solid‐state diffusion by 12.2 % and increased surface‐limitations by 17.0 % (stable samples). This approach enabled retaining 95 % lithiation capacity at ∼800 mV s −1 (1,600 C‐rate equivalent).

25 ENERGY STORAGE↗
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↗
DOE OSTI2021

Wafer-scale quasi-layered tungstate-doped polypyrrole film with high volumetric capacitance

Layered materials are particularly attractive for supercapacitors because of their unique physical, electrical and chemical properties. In this work, we demonstrate a facile and scalable electrochemical deposition method for wafer-scale synthesis of quasi-layered tungstate-doped polypyrrole films (named TALPy) with controllable thickness and size. The as-prepared TALPy film exhibits a high gravimetric density and excellent volumetric capacitance, exceeding many high-performing carbon- and polymer-based film electrodes. Based on combined results of ex-situ X-ray diffraction (XRD), Raman and X-ray photoelectron spectroscopy (XPS), it is determined that TALPy stores charge through an ion intercalation process accompanied by change in oxidation states of polypyrrole backbone, which is referred as intercalation pseudocapacitance. All these results suggest the great promise of electrochemical deposition as a scalable and controllable bottom-up approach for synthesizing quasi-layered conductive organic-inorganic hybrid films for electrochemical energy storage applications with high volumetric performance.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Tailoring solid-electrolyte interphase and solvation structure for subzero temperature, fast-charging, and long-cycle-life sodium-ion batteries

The sluggish Na + reaction kinetics with carbon materials limits the fast-charging capability, Coulombic efficiency, and cycle life of sodium-ion batteries, especially at low temperatures. Herein, free-standing carbon nanofiber films, with controllable crystallinity and surface chemistry, are used as a platform to investigate the correlation between Na + reaction kinetics, storage mechanism, and electrolyte environment. The ion solvation effect and solid-electrolyte interphase (SEI) properties determine the kinetics and storage mechanism. A strong Na + -solvent interaction, such as Na + -diglyme, tends to form a "pseudo-SEI" layer dominated by anion decomposition, enabling fast Na + -solvent co-intercalation kinetics. Tuning the SEI chemistries by pre-cycling in the weakly solvated electrolyte (e.g., ester electrolyte), the intercalation capacity rapidly disappears due to the high energy barrier for Na + transport. Finally, such mechanistic insights allow us to develop the optimal combination of electrode materials and electrolyte chemistry to achieve high initial Coulombic efficiency, ultra-long cycle life under fast charging, and excellent low-temperature performance.

25 ENERGY STORAGE↗
DOE OSTI2022

Breaking of Inversion Symmetry and Interlayer Electronic Coupling in Bilayer Graphene Heterostructure by Structural Implementation of High Electric Displacement Fields

Controlling the interlayer coupling in two-dimensional (2D) materials generates novel electronic and topological phases. Its effective implementation is commonly done with a transverse electric field. However, phases generated by high displacement fields are elusive in this standard approach. Here, we introduce an exceptionally large displacement field by structural modification of a model system: AB-stacked bilayer graphene (BLG) on a SiC(0001) surface. We show that upon intercalation of gadolinium, electronic states in the top graphene layers exhibit a significant difference in the on-site potential energy, which effectively breaks the interlayer coupling between them. As a result, for energies close to the corresponding Dirac points, the BLG system behaves like two electronically isolated single graphene layers. This is proven by local scanning tunneling microscopy (STM)/spectroscopy, corroborated by density functional theory, tight binding, and multiprobe STM transport. Further, the work presents metal intercalation as a promising approach for the synthesis of 2D graphene heterostructures with electronic phases generated by giant displacement fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Role of Heterointerface in Lithium-Induced Phase Transition in T d -WTe 2 Nanoflakes

A new polytype of WTe 2 with a bandgap has been recently discovered through the intercalation of lithium into the van der Waals gaps of T d -WTe 2 . Here, we report the effects of reduced thicknesses and heterointerfaces on the intercalation-induced phase transition in WTe 2 . Using in situ Raman spectroscopy during the electrochemical lithiation of WTe 2 flakes as a function of flake thickness, we observe that additional electrochemical energy is required for the phase transition of WTe 2 from the T d phase to the new lithiated T d ' phase, going from 0.8 V of the applied electrochemical voltage for a thick flake to 0.5 V and 0.3 V for 7- and 5-layered samples, respectively. We ascribe this suppression of the phase transition to the interfacial interaction between the nanoflake and SiO 2 /Si substrate, which plays an increasing role as the sample thickness is reduced. The suppressed kinetics of the phase transition can be mitigated by placing the WTe 2 flake on a hexagonal boron nitride (hBN) flake, which facilitates the release of the in-plane strain induced by the phase transition. Importantly, our study underscores the significance of interfacial effects in modulating phase transitions in two-dimensional (2D) materials, suggesting heterogeneous transition pathways, as well as interfacial engineering to control these phase transitions.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Reaction Mechanism of Electrodeposited ε-MnO 2 : A Proton-Centered Pathway in Aqueous Zn-Ion Systems

Aqueous Zn/MnO 2 batteries have garnered significant interests owing to their abundance, high theoretical specific capacity, safety, and low cost. However, large-scale application of these systems is limited by the incomplete understanding of the MnO 2 reaction chemistry. The different crystal lattice structures among MnO 2 polymorphs contribute to the variations in reported reaction mechanisms. Among them, ε-MnO 2 polymorph, the dominant phase in electrolytic manganese dioxide (EMD), is notably observed during the charge cycles of aqueous Zn/MnO 2 batteries. Here, in this work, we investigate the electrochemical behavior of an ε-MnO 2 cathode synthesized via electrodeposition from a ZnSO 4 and MnSO 4 electrolyte, onto a 3-dimensional carbon cloth substrate. Proton intercalation emerges as the dominant charge storage mechanism, critically enabling the reversibility of ε-MnO 2 during cycling, as revealed by operando synchrotron X-ray diffraction and X-ray absorption spectroscopy. Additionally, a proton-coupled dissolution/redeposition pathway operates alongside minor Zn 2+ intercalation, as quantified by Rietveld refinement. Morphological and chemical heterogeneities are studied by transmission X-ray microscopy further validates this reaction mechanism. These mechanistic insights provide the foundation for rationally designing Zn/MnO 2 batteries with optimized proton dynamics and charge transfer, advancing these systems as a viable solution for safe, cost-effective grid-scale energy storage.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Switchable Charge Storage Mechanism via in Situ Activation of MXene Enables High Capacitance and Stability in Aqueous Electrolytes

The need for reliable renewable energy storage devices has become increasingly important. However, the performance of current electrochemical energy storage devices is limited by either low energy or power densities and short lifespans. Herein, we report the synthesis and characterization of multilayer Ti 4 N 3 T x MXene in various aqueous electrolytes. We demonstrate that Ti 4 N 3 T x can be electrochemically activated through continuous cation intercalation over a 10 day period using cyclic voltammetry. A wide operating window of 2 V is maintained throughout activation. After activation, capacitance at 2 mV s -1 increases by 300%, 140%, and 500% in 1 M H2SO4, 1 M MgSO4, and 1 M KOH, respectively, while maintaining ~600 F g -1 at 2 mV s–1 after 50000 cycles in 1 M H 2 SO 4 . This activation process is possibly attributed to the unique morphology of the multilayered material, allowing cation intercalation to increase access to redox-active sites between layers. This work adds to the growing repository of electrochemically stable MXenes reported for aqueous energy storage applications. These findings offer a reliable option for reliable energy storage devices with potential applications in large-scale grid storage and electric vehicles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗