SEARCH · Search NASA

Results for “intercalations”

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.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 109 records · Page 6

All sources NASA NTRS DOE OSTI

DOE OSTI2025

Structure–property relationships of reduced graphene oxide membranes intercalated with polycyclic aromatics

Graphene oxide (GO) membranes intercalated with various organic moieties have shown excellent potential for a range of water processing applications. However, microstructure–functional property relationships in these structurally disordered membranes are not well understood. We demonstrate a practical methodology for developing such relationships for GO membranes intercalated with molecular species, with polycyclic aromatic toluidine blue O (TBO) as an example functional intercalant. We use solid-state UV–vis absorbance and fluorescence measurements to quantitatively track the arrangements of TBO in a series of TBO-loaded reduced GO (rGO) membranes. This study reveals the evolution of diverse arrangements including TBO monomers, lateral and stacked dimers, and other aggregates, as a function of overall TBO loading. These microstructures are then correlated to changes in overall properties such as interlayer d-spacings, permeate fluxes, and solute rejections. The characterization of these different intercalant microstructures explains non-intuitive flux and rejection trends, which can circumvent flux and solute rejection trade-offs.

02 PETROLEUM↗

DOE OSTI2022

Elucidating structure and dynamics of crystalline α-zirconium phosphates intercalated with water and methanol by multinuclear solid-state MAS NMR: A comprehensive NMR approach

Solid-state NMR experiments on 2 H, 31 P, 13 C, and 1 H nuclei, including 31 P T 1 , 1 H T 1 , and 1 H T 1ρ measurements, as well as on the kinetics of proton-phosphorus cross-polarization have been performed to characterize the crystalline and amorphous α-zirconium phosphates, which were intercalated with D 2 O and/or CD 3 OD. The 13 C{ 1 H} CP MAS NMR experiment performed for compound 1-CD 3 OD (Zr (HPO 4 ) 2 .0.2CD 3 OD) with carbon cross-polarization via protons of phosphate groups has provided a prove that the methanol was intercalated into the interlayer spaces of this compound. The variable-temperature 2 H solid-echo MAS NMR spectra of intercalated compounds demonstrated that the methanol molecules, in contrast to the mobile water, were immobile, keeping, however, free CD 3 rotations around the C 3 -axis. It has been demonstrated that the intercalated species, D 2 O and CD 3 OD, do not affect the high-frequency motions of the phosphate groups. By utilizing local structural models that satisfy the constraints of the experimental data, it has been suggested that the immobile methanol molecules are located in the cavity between two neighboring layers of the zirconium phosphates. Here, the present work illustrates the reliable criteria in a comprehensive NMR approach to structural and dynamic studies of such systems.

1H↗

DOE OSTI2020

NASICON Na 3 V 2 (PO 4 ) 3 Enables Quasi-Two-Stage Na + and Zn 2+ Intercalation for Multivalent Zinc Batteries

Identifying positive electrode materials capable of reversible multivalent electrochemistry in electrolytes containing divalent ions such as Mg 2+ , Ca 2+ , and Zn 2+ at high operating potentials remains an ongoing challenge in “beyond lithium-ion” research. In this paper, we explore the Zn 2+ charge-storage mechanism of a vanadium-based Na + superionic conductor (NASICON), Na 3 V 2 (PO 4 ) 3 . By using X-ray synchrotron techniques to unravel potential-dependent structure–property relationships, we ascribe the reversible electrochemical behavior of Na 3 V 2 (PO 4 ) 3 to a quasi-two-stage intercalation process that involves both Na+ and Zn 2+ . Initial charging of Na 3 V 2 (PO 4 ) 3 leads to a Na + -extracted phase corresponding to Na 3 V 2 (PO 4 ) 3 , whereas subsequent discharge results predominantly in Na + intercalation followed by Zn 2+ intercalation. Operando X-ray diffraction of Na 3 V 2 (PO 4 ) 3 was used to study the phase changes associated with the first charge/discharge process, and ex situ measurements were used to precisely link the changes in the crystal structure to a quasi-two-stage intercalation of Na + and Zn 2+ . The corresponding changes in the V-oxidation state, V-O coordination, and the presence of Zn 2+ were confirmed by X-ray absorption spectroscopy. The results of this work present a comprehensive understanding of the charge-storage properties for a well-established NASICON structure that confers both the high capacity (~100 mA h g -1 ) and high potential (1.35 and 1.1 V vs Zn/Zn 2+ ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Intercalation-Engineered Out-of-Plane Polarized van der Waals Ferromagnetic Superlattice with Room-Temperature Néel-Type Skyrmions

Superlattices (SLs) based on two-dimensional (2D) van der Waals (vdW) materials, abbreviated as 2D-SLs, have garnered significant attention due to their customizable properties. 2D-SLs can be engineered by mechanical stacking or chemical intercalation to achieve diverse forms of symmetry breaking, resulting in exotic phenomena like the quantum anomalous Hall effect and topological magnetism. Hitherto, broken symmetries in 2D-SLs have been widely produced within lateral planes or three dimensions. However, symmetry breaking along the vertical direction, specifically as an out-of-plane one-dimensional (1D) polarized superlattice, has not yet been achieved. Here, in this paper, we report a so far unseen out-of-plane 1D polarized vdW ferromagnetic superlattice achieved through an approach of two-step intercalation and de-embedding of chromium (Cr)-based 2D vdW magnets. The off-centering polarization of both intrinsic and intercalated Cr atoms in this (1 × 1 × 2) superstructure breaks the mirror symmetry vertically, yielding a Dzyaloshinskii–Moriya interaction (DMI). This results in high-density Néel-type magnetic skyrmions over a broad temperature range. Notably, sub-100 nm Néel-type skyrmions at room temperature (RT) can be achieved by tuning the Cr intercalation ratio, marking the first binary compound RT Néel-type skyrmionic vdW magnet. Our work expands the 2D-SL family with a class of out-of-plane 1D polarized ferromagnetic superlattice with tunable topological magnetism.

1D polarized superlattice↗

DOE OSTI2026

Topochemical Oxidation of Ruddlesden–Popper Nickelates Reveals Distinct Structural Family: Oxygen-Intercalated Layered Perovskites

Layered perovskites─including the Dion–Jacobson, Ruddlesden–Popper, and Aurivillius families─exhibit a wide range of correlated electron phenomena, from high-temperature superconductivity to multiferroicity. Here, in this study, we report a new family of layered perovskites realized through topochemical oxidation of La n+1 Ni n O 3n+1+δ (n = 1–4) Ruddlesden–Popper nickelate thin films. Postgrowth ozone annealing induces a substantial c-axis expansion─17.8% for La 2 NiO 4+δ (n = 1)─that monotonically decreases with increasing n. Surface synchrotron X-ray diffraction and coherent Bragg rod analysis (COBRA) reveal that this structural expansion arises from the intercalation of approximately δ ≈ 0.7–1.0 oxygen atoms into interstitial sites within the rock salt spacer layers, far exceeding the previous record of δ ≈ 0.3 for any Ruddlesden–Popper oxide. These oxygen-intercalated phases form a new class of layered perovskites with a spacer layer composition intermediate between the Ruddlesden–Popper and Aurivillius phases. Furthermore, oxygen intercalation induces metallicity, enhances nickel–oxygen hybridization, and suppresses oxygen octahedral rotations, a feature associated with high-temperature superconductivity in Ruddlesden–Popper nickelates. Our work establishes topochemical oxidation as a powerful approach to accessing highly oxidized, metastable phases across a broad range of layered oxide systems, offering new platforms to engineer electronic properties via intercalation chemistry.

Ferenc Segedin, Dan [Harvard Univ., Cambridge, MA ↗

DOE OSTI2025

Tailored topotactic chemistry unlocks heterostructures of magnetic intercalation compounds

The construction of thin film heterostructures has been a widely successful archetype for fabricating materials with emergent physical properties. This strategy is of particular importance for the design of multilayer magnetic architectures in which direct interfacial spin-spin interactions between magnetic phases in dissimilar layers lead to emergent and controllable magnetic behavior. However, crystallographic incommensurability and atomic-scale interfacial disorder can severely limit the types of materials amenable to this strategy, as well as the performance of these systems. Here, we demonstrate a method for synthesizing heterostructures comprising magnetic intercalation compounds of transition metal dichalcogenides (TMDs), through directed topotactic reaction of the TMD with a metal oxide. The mechanism of the intercalation reaction enables thermally initiated intercalation of the TMD from lithographically patterned oxide films, giving access to a family of multi-component magnetic architectures through the combination of deterministic van der Waals assembly and directed intercalation chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Magnetic properties of intercalated quasi-2D Fe 3-x GeTe 2 van der Waals magnet

Among several well-known transition metal-based compounds, cleavable van der Waals (vdW) Fe 3-x GeTe 2 (FGT) magnet is a strong candidate for use in two-dimensional (2D) magnetic devices due to its strong perpendicular magnetic anisotropy, sizeable Curie temperature (T C ~154 K), and versatile magnetic character that is retained in the low-dimensional limit. While the T C remains far too low for practical applications, there has been a successful push toward improving it via external driving forces such as pressure, irradiation, and doping. Here we present experimental evidence of a room temperature (RT) ferromagnetic phase induced by the electrochemical intercalation of common tetrabutylammonium cations (TBA+) into quasi-2D FGT. We obtained Curie temperatures as high as 350 K with chemical and physical stability of the intercalated compound. The temperature-dependent Raman measurements, in combination with vdW-corrected ab initio calculations, suggest that charge transfer (electron doping) upon intercalation could lead to the observation of RT ferromagnetism. This work demonstrates that molecular intercalation is a viable route in realizing high-temperature vdW magnets in an inexpensive and reliable manner and has the potential to be extended to bilayer and few-layer vdW magnets.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2023

Enumeration of Moiré patterns of a hexagonal twisted bilayer: Applications to intercalated transition metals

A real-space method using generating integers is used to determine possible commensurate lattice Moiré patterns for a bilayer of two equal hexagonal lattices, which can in principle be extended to lattice mismatched bilayers. These Moiré patterns can be classified by a pair of relatively prime integers (n,m), wherein a rotation θ(n,m) of the top hexagonal lattice maps its lattice vector (n,m) to (m,n) of the bottom lattice. Within this formulation, the area of the commensurate supercell is proportional to (n2+m2+nm) and the number of coincident lattice sites per supercell is given by (n−m)2. Taking bilayer boron nitride (BN) as an example, we present how to systematically generate Moiré patterns and explore the differences in local chemistry in the interstitial region by impurity intercalation. Systematic calculations of the properties of intercalated 3d transition metals were performed in an h-BN (4,3) bilayer, corresponding to a rotation of 9.43 degrees. These calculations reveal that local symmetry in the intercalated region significantly affect the energetics and magnetization of the intercalated species. These results highlight that Moiré pattern physics is not limited to optoelectronic/electronic phenomena, such as interfacial exciton formation or magic angle superconductivity, but it also produces chemical and magnetic atomic site selectivity, which may play important roles in adsorption, catalysis, or quantum information.

Physics↗

DOE OSTI2022

Emergence of ferrimagnetism in Li-intercalated NiPS 3

AbstractIntercalation has become a powerful approach to tune the intrinsic properties and introduce novel phenomena in layered materials. Intercalating van der Waals (vdW) magnetic materials is a promising route to engineer the low-dimensional magnetism. Recently, metal thiophosphates, MPX 3 , has been widely studied because their magnetic orders are highly tunable and persist down to the two-dimensional limit. In this work, we used electrochemical technique to intercalate Li into NiPS 3 single crystals and found the emergence of ferrimagnetism at low temperature in Li-intercalated NiPS 3 . Such tuning of magnetic properties highlights the effectiveness of intercalation, providing a novel strategy to manipulate the magnetism in vdW magnets.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2021

Manipulation of electronic property of epitaxial graphene on SiC substrate by Pb intercalation

Manipulating the electronic properties of graphene has been a subject of great interest since it can aid material design to extend the applications of graphene to many different areas. Here, we systematically investigate the effect of lead (Pb) intercalation on the structural and electronic properties of epitaxial graphene on the SiC(0001) substrate. We show that the band structure of Pb-intercalated few-layer graphene can be effectively tuned through changing intercalation conditions, such as coverage, location of Pb, and the initial number of graphene layers. Lead intercalation at the interface between the buffer layer (BL) and the SiC substrate decouples the BL from the substrate and transforms the BL into a p-doped graphene layer. We also show that Pb atoms tend to donate electrons to neighboring layers, leading to an n-doping graphene layer and a small gap in the Dirac cone under a sufficiently high Pb coverage. This paper provides useful guidance for manipulating the electronic properties of graphene layers on the SiC substrate.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Enhanced superconductivity and electron correlations in intercalated ZrTe 3

We report charge density waves (CDWs) with superconductivity, competing Fermi surface instabilities, and collective orders have captured much interest in two-dimensional van der Waals (vdW) materials. Understanding the CDW suppression mechanism, its connection to the emerging superconducting state, and electronic correlations provides opportunities for engineering the electronic properties of vdW heterostructures and thin-film devices. Using a combination of the thermal transport, x-ray photoemission spectroscopy, Raman measurements, and first-principles calculations, we observe an increase in electronic correlations of the conducting states as the CDW is suppressed in ZrT e3 with 5% Cu and Ni intercalation in the vdW gap. As superconductivity emerges, intercalation brings not only decoupling of quasi-one-dimensional conduction electrons with phonons as a consequence of intercalation-induced lattice expansion but also a drastic increase in Zr 2+ at the expense of Zr 4+ metal atoms. These observations not only demonstrate the potential of atomic intercalates in the vdW gap for ground-state tuning but also illustrate the crucial role of the Zr metal valence in the formation of collective electronic orders.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2020

Growth and stability of Pb intercalated phases under graphene on SiC

Graphene intercalation is a novel way to control graphene's band structure and generate two-dimensional quantum materials with unusual spintronic and electronic properties. In spite of its importance, information about the intercalation mechanism is lacking, especially the role of low density domain boundaries between regions of graphene of different thickness. With high resolution surface diffraction we have systematically studied Pb intercalation on epi-graphene grown on SiC, with domain boundaries between buffer and single layer graphene. By examining the evolution of different diffraction spots as a function of tempertature, the location of Pb and stability of the intercalated phases underneath were determined.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Electrode strain dynamics in layered intercalation battery cathodes

Rechargeable batteries using electrodes based on intercalation chemistry exhibit notable cyclability, yet their performance still suffers from chemomechanical degradation. In this study, by combining a suite of operando microscopy methods, we explored electrode strain evolution and observed intricate particle cluster rearrangement under electrochemical stimuli. We show that early-stage strain accumulation in intercalation cathodes occurs during the period of interparticle charge transfer and redox reactions stemming from asynchronous coupling and decoupling between chemical (de)intercalation and physical grain motion. This interplay drives heterogeneous redox activity, localized charge equilibration, and multiscale strain cascades that propagate through an asynchronous network of chemical-mechanical interactions. Together, these findings reveal how collective particle dynamics and hierarchical strain transmission dictate electrode deformation and degradation in intercalation cathodes.

25 ENERGY STORAGE↗

NASA NTRS1985

A micrographic and gravimetric study of intercalation and deintercalation of graphite fibers

Intercalation and deintercalation of Union Carbide P-100 graphite fibers with liquid and vaporous bromine was studied gravimetrically and microscopically. The mass of the bromine intercalated fibers was found to be 17 to 20 percent greater than their pristine counterpart. This variation decreased to 17 to 18 percent after heating in air for 3 days at 200 C and to 14.5 to 18 percent after 6 days of 260 C heating. The fiber length did not change throughout the experiment. The fiber diameter increased during intercalation and decreased slightly upon deintercalation but was not affected by heating to 260 C for 3 days in air. Comparing the mass and volume data to those with highly oriented pyrolitic graphite or natural single crystal graphite suggested the possibility that the intercalated P-100 fibers could be mostly stage 4.

Hung, C. C.↗

NASA NTRS1989

Density of intercalated graphite fibers

The density of Amoco P-55, P-75, P-100, and P-120 pitch-based graphite fibers and their intercalation compounds with bromine, iodine monochloride, and copper (II) chloride have been measured using a density gradient column. The distribution of densities within a fiber type is found to be a sensitive indicator of the quality of the intercalation reaction. In all cases the density was found to increase, indicating that the mass added to the graphite is dominant over fiber expansion. Density increases are small (less than 10 percent) giving credence to a model of the intercalated graphite fibers which have regions which are intercalated and regions which are not.

Gaier, James R.↗

NASA NTRS1990

Density of intercalated graphite fibers

Gaier, James R.↗

NASA NTRS1999

Intercalation of Lithium in Pitch-Based Graphitized Carbon Fibers Chemically Modified by Fluorine: Soft Carbon With or Without an Oxide Surface

The effects of carbon structure and surface oxygen on the carbon's performance as the anode in lithium-ion battery were studied. Two carbon materials were used for the electrochemical tests: soft carbon made from defluorination of graphite fluoride, and the carbon precursor from which the graphite fluoride was made. In this research the precursor was graphitized carbon fiber P-100. It was first fluorinated to form CF(0.68), then defluorinated slowly at 350 to 450 C in bromoform, and finally heated in 1000 C nitrogen before exposed to room temperature air, producing disordered soft carbon having basic surface oxides. This process caused very little carbon loss. The electrochemical test involved cycles of lithium intercalation and deintercalation using C/saturated LiI-50/50 (vol %) EC and DMC/Li half cell. The cycling test had four major results. (1) The presence of a basic oxide surface may prevent solvent from entering the carbon structure and therefore prolong the carbon's cycle life for lithium intercalation-deintercalation. (2) The disordered soft carbon can store lithium through two different mechanisms. One of them is lithium intercalation. which gives the disordered carbon an electrochemical behavior similar to its more ordered graphitic precursor. The other is unknown in its chemistry, but is responsible for the high-N,oltage portion (less than 0.3V) of the charge-discharge curve. (3) Under certain conditions, the disordered carbon can store more lithium than its precursor. (4) These sample and its precursor can intercalate at 200 mA/g. and deintercalate at a rate of 2000 mA/g without significant capacity loss.

Hung, Ching-Chen↗

NASA NTRS2014

Exfoliation of Hexagonal Boron Nitride via Ferric Chloride Intercalation

Sodium fluoride (NaF) was used as an activation agent to successfully intercalate ferric chloride (FeCl3) into hexagonal boron nitride (hBN). This reaction caused the hBN mass to increase by approx.100 percent, the lattice parameter c to decrease from 6.6585 to between 6.6565 and 6.6569 Ǻ, the x-ray diffraction (XRD) (002) peak to widen from 0.01deg to 0.05deg of the full width half maximum value, the Fourier transform infrared (FTIR) spectrum's broad band (1277/cm peak) to change shape, and new FTIR bands to emerge at 3700 to 2700 and 1600/cm. This indicates hBN's structural and chemical properties are significantly changed. The intercalated product was hygroscopic and interacted with moisture in the air to cause further structural and chemical changes (from XRD and FTIR). During a 24-h hold at room temperature in air with 100 percent relative humidity, the mass increased another 141 percent. The intercalated product, hydrated or not, can be heated to 750 C in air to cause exfoliation. Exfoliation becomes significant after two intercalation-air heating cycles, when 20-nm nanosheets are commonly found. Structural and chemical changes indicated by XRD and FTIR data were nearly reversed after the product was placed in hydrochloric acid (HCl), resulting in purified, exfoliated, thin hBN products.

Hung, Ching-cheh↗