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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Competitive formation of intercalated versus supported metal nanoclusters during deposition on layered materials with surface point defects

Intercalated metal nanoclusters (NCs) can be formed under the surface of graphite after sputtering to generate surface “portal” defects that allow deposited atoms to reach the subsurface gallery. Although, there is a competition between formation of supported NCs on top of the surface and intercalated NCs under the surface, the latter only dominating at sufficiently high temperature. A stochastic model incorporating appropriate system thermodynamics and kinetics is developed to capture this complex and competitive nucleation and growth process. Kinetic Monte Carlo simulation shows that the model captures experimental trends observed for Cu and other metals and reveals that higher temperatures are needed to facilitate detachment of atoms from supported NCs enabling them to reach the gallery.

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

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↗
DOE OSTI2025

Charge Density Wave and Ferromagnetism in Intercalated CrSBr

In materials with 1D electronic bands, electron–electron interactions can produce intriguing quantum phenomena, including spin-charge separation and charge density waves (CDW). Most of these systems, however, are non-magnetic, motivating a search for anisotropic materials where the coupling of charge and spin may affect emergent quantum states. Here, in this study, chemical intercalation of the van der Waals magnetic semiconductor CrSBr yields Li 0.17(2) (tetrahydrofuran) 0.26(3) CrSBr, which possesses an electronically driven quasi-1D CDW with an onset temperature above room temperature. Concurrently, electron doping increases the magnetic ordering temperature from 132 to 200 K and switches its interlayer magnetic coupling from antiferromagnetic to ferromagnetic. The spin-polarized nature of the anisotropic bands that give rise to this CDW enforces an intrinsic coupling of charge and spin. The coexistence and interplay of ferromagnetism and charge modulation in this exfoliatable material provide a promising platform for studying tunable quantum phenomena across a range of temperatures and thicknesses.

2D magnets↗
DOE OSTI2020

Equilibrium shapes of facetted 3D metal nanoclusters intercalated near the surface of layered materials

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.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Asphericity Can Cause Nonuniform Lithium Intercalation in Battery Active Particles

Uniform intercalation is desired to enable next-generation Li-ion batteries. While we expect nonuniformity in materials undergoing a phase change, single-phase intercalation materials such as nickel manganese cobalt oxide are believed to lithiate uniformly at the particle/electrolyte interface. However, recent imaging reveals nonuniform lithiation. Motivated by this discrepancy, we examine if aspherical particle shape can cause such nonuniformity since the conventional belief is based on spherical particle theory. We obtain real particle geometries using rapid lab-based X-ray computed tomography and subsequently perform physics-based calculations accounting for electrochemical reactions at the particle/electrolyte interface and lithium transport inside the particle bulk. The aspherical geometry breaks the symmetry and causes nonuniform reaction distribution. Such nonuniformity is exacerbated as the particle becomes more aspherical. We report the proposed mechanism represents a fundamental limit on achievable lithiation uniformity in aspherical particles in the absence of other mechanisms causing inhomogeneity, such as grain structure, nonuniform carbon-binder coating, etc.

25 ENERGY STORAGE↗
DOE OSTI2025

Valuation of Anode Materials for High-Performance Lithium Batteries: From Graphite to Lithium Metal and Beyond

Lithium-ion batteries have revolutionized energy storage, yet advanced technologies such as electric vehicles and eVTOLs demand even higher performance and safety. Anodes, the negative electrodes, are crucial in enhancing batteries’ safety, lifespan, and fast-charging capabilities. This review paper comprehensively evaluates the progression of anode materials from traditional graphite to advanced anodes like lithium metal. Graphite anodes, with a capacity of 372 mAh g −1 , enabled the first commercial lithium-ion batteries, but future applications require higher energy densities and fast-charging capabilities. Emerging anode materials, including alloying, and conversion types, as well as lithium metal, offer significantly higher capacities, with lithium metal offering a theoretical capacity of 3 860 mAh g −1 . However, these advanced anodes face challenges such as volume expansion, high surface reactivity, sluggish Li+ kinetics, and unstable lithium deposition morphologies. Here, this review critically examines the electrochemical performance, interfacial properties, mechanical attributes, and stability issues of various anode materials. It further discusses solid electrolyte interphase (SEI) formation, strategies for enhancing interface stability, and the requirements of anodes for solid-state batteries. Additionally, the review explores potential solutions for limitations with each anode type, highlights innovative anode-free architectures, and evaluates the current and future trends of battery anode industries. Ultimately, this paper aims to guide the development of high-performance anode materials, paving the way for the next generation of efficient, reliable lithium batteries.

Alloying anodes↗
DOE OSTI2025

Quantum Monte Carlo Approaches to Na Intercalation on Bilayer Graphene

We have performed Quantum Monte Carlo (QMC) simulations on Na-intercalated bilayer graphene to study the evolution of electronic and optical properties upon Na intercalation into hard carbon layers. The objective was to model the optimal configuration of Na intercalation into a hard carbon matrix containing graphene regions. Our study showed that Na intercalation can be energetically stabilized at large interlayer distances (over 6 Å) in both AA- and AB-stacked bilayer graphene. In the QMC results, we found a significant band gap opening at the equilibrium interlayer distance of Na-intercalated bilayer graphene, while corresponding density functional theory (DFT) results showed no gap. This difference between DFT and QMC results indicates that the gap opening induced by Na intercalation into a hard carbon is underestimated within the DFT framework. In addition, a zigzag configuration of Na atoms was found to be energetically stable at interlayer distances up to 10 Å, leading us to predict the existence of a local minimum of Na intercalation at large interlayer distance. These computation and modeling results can provide guidance on how to synthesize and optimize hard carbon with bilayer graphene regions that permit a zigzag intercalation configuration that will maximize and stabilize sodium hosting.

Binding energy↗
DOE OSTI2020

On the Remarkable Superconductivity of FeSe and Its Close Cousins

Emergent electronic phenomena in iron-based superconductors have been at the forefront of condensed matter physics for more than a decade. Much has been learned about the origins and intertwined roles of ordered phases, including nematicity, magnetism, and superconductivity, in this fascinating class of materials. In recent years, focus has been centered on the peculiar and highly unusual properties of FeSe and its close cousins. This family of materials has attracted considerable attention due to the discovery of unexpected superconducting gap structures, a wide range of superconducting critical temperatures, and evidence for nontrivial band topology, including associated spin-helical surface states and vortex-induced Majorana bound states. Here, we review superconductivity in iron chalcogenide superconductors, including bulk FeSe, doped bulk FeSe, FeTe1−xSex, intercalated FeSe materials, and monolayer FeSe and FeTe1−xSex on SrTiO3. We focus on the superconducting properties, including a survey of the relevant experimental studies, and a discussion of the different proposed theoretical pairing scenarios. In the last part of the paper, we review the growing recent evidence for nontrivial topological effects in FeSe-related materials, focusing again on interesting implications for superconductivity.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Evaluating Material Design Principles for Calcium-Ion Mobility in Intercalation Cathodes

Multivalent-ion batteries offer an alternative to Li-based technologies, with the potential for greater sustainability, improved safety, and higher energy density, primarily due to their rechargeable system featuring a passivating metal anode. Although a system based on the Ca 2+ /Ca couple is particularly attractive given the low electrochemical plating potential of Ca 2+ , the remaining challenge for a viable rechargeable Ca battery is to identify Ca cathodes with fast ion transport. In this work, a high-throughput computational pipeline is adapted to (1) discover novel Ca cathodes in a largely unexplored space of empty intercalation hosts and (2) develop material design rules for Ca-ion mobility. One candidate from the screening, W 2 O 3 (PO 4 ) 2 , is confirmed to have a low Nudged Elastic Band (NEB) barrier of 168 meV within a one-dimensional (1D) ion percolation topology. This candidate is subsequently synthesized and electrochemically tested, achieving reversible Ca cycling with a capacity of 25 mA h/g. To further accelerate the screening for promising Ca intercalation electrodes, machine learning (ML) Random Forest (RF) and Extreme Gradient Boosting (XGB) classification models are created with local environment descriptors based on a large, structurally and chemically diverse dataset of minimum energy pathways, spanning over 5,000 density functional theory (DFT) site energy calculations. Accuracies of 92% are achieved, material design metrics are quantified, ML force-fields are leveraged in an accelerated iteration of the screening, and a total of 27 novel Ca cathode materials are highlighted for further investigation.

25 ENERGY STORAGE↗
DOE OSTI2023

Intercalation And High-Pressure Effects On Structural Phase Transitions In Layered As x P 1-x Alloys

This project was aimed at understanding the role of composition, intercalation, and high pressure on the structural evolution of black phosphorous (BP) and layered arsenic phosphorous alloys, As y P 1-y . Under normal conditions, BP is the most stable phase of phosphorous, known as the α-phase, characterized by an orthorhombic honeycomb puckered crystal structure with the Cmca space group. On the other hand, the most stable phase of arsenic is its β-phase, known as gray arsenic (g-As), which has a rhombohedral buckled layered crystal structure with the R3m space group. In a wide range of compositions (y < 0.83), the arsenic phosphorous alloys form the α-phase, known as black arsenic phosphorous (b-As y P 1-y ) with a similar structure to BP. The project was aimed at the synthesis of BP and b-As y P 1-y with different compositions and at studying the structural evolution of these materials during intercalation with alkali metal (especially Li), and under high-pressure conditions. The main goals were to gain a better understanding of these processes and structural changes taking place under these conditions. In particular, the project was aimed at addressing whether such conditions could induce a structural transition between the α- and β-phases. For this, a series of systematic in-situ studies were conducted, including electrochemical lithium intercalation in an in-situ electrochemical cell, and high-pressure experiments in a diamond anvil cell (DAC). Overall, both types of experiments have shown that above a certain composition-dependent threshold level of intercalation or high pressure, the system undergoes phase segregation rather than phase transition. Specifically, the segregation of the excess arsenic was observed, and a single-phase system of b-As y P 1-y transformed into a two-phase system consisting of b-As y P 1-y and g-As, through the following process: 1∗(b-As y P 1-y ) → 1∗(b As y-δ P 1-y ) + δ∗(g-As). Also, the study showed that intercalation and high-pressure are two competing rather than synergistic processes causing at least a partial cancelation of these two factors

36 MATERIALS SCIENCE↗
DOE OSTI2023

A review of transport models in charged porous electrodes

There is increased interest in many different processes based upon interactions between a charged solid surface and a liquid electrolyte. Energy storage in capacitive porous materials, ionic membranes, capacitive deionization (CDI) for water desalination, capacitive energy generation, removal of heavy ions from wastewater streams, and geophysical applications are some examples of these processes. Process development is driven by the production of porous materials with increasing surface area. Understanding of the physical phenomena occurring at the charged solid-electrolyte interface will significantly improve the design and development of more effective applied processes. The goal of this work is to critically review the current knowledge in the field. The focus is on concepts behind different models. We start by briefly presenting the classical electrical double layer (EDL) models in flat surfaces. Then, we discuss models for porous materials containing macro-, meso-, and micro-pores. Some of the current models for systems comprising two different pore sizes are also included. Finally, we discuss the concepts behind the most common models used for ionic transport and Faradaic processes in porous media. The latter models are used for simulation of electrosorption processes in porous media.

42 ENGINEERING↗
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 OSTI2024

The Hard Ferromagnetism in FePS 3 Induced by Non‐Magnetic Molecular Intercalation

Abstract Manipulating the magnetic ground states of 2D magnets is a focal point of recent research efforts. Various methods have demonstrated efficacy in modulating the magnetic properties inherent to van der Waals (vdW) magnetic systems. Herein, the emergence of robust anisotropic ferromagnetism within antiferromagnetic FePS 3 is unveiled via intercalation with non‐magnetic pyridinium ions. A one‐step ion exchange reaction facilitates the formation of energetically favorable B‐phase and metastable P‐phase. Notably, both B‐ and P‐phases manifest hard ferromagnetic behavior, featuring substantial unsaturated coercive fields (>7 T) and high Curie temperatures (72–87 K). First‐principles calculations elucidate the pivotal role of electron transfer from pyridinium ions to FePS 3 in engineering magnetic exchange interactions. Calculated effective spin Hamiltonian corroborates the observed hard ferromagnetism in intercalated FePS 3 . This study offers crucial insights into hard magnetism in intercalated vdW materials, thereby presenting promising avenues for 2D vdW magnet‐based magnetic devices.

Ou, Yunbo↗
DOE OSTI2025

Simplified calculation of the area specific impedance for solid-state battery design

Simplified algebraic area specific impedance (ASI) correlations have been developed for solid-state composite battery electrodes made of a single ion conducting electrolyte, conductive additive, and intercalation active material. Two ASI expressions were developed, one for short times ( i.e. , pulsed power operation) and another for the pseudo steady state operation (i.e., sustained discharge for energy estimation). A full electrochemical model based on porous electrode theory was developed to examine the accuracy of the simplified ASI expressions. The simplified expressions agree favorably with full model results over a wide range of parameters (i.e. , electrode thicknesses, electrolyte conductivities, solid-state diffusion coefficients, specific surface areas, etc.) and conditions (i.e. , C-rates, states of charge, and pulse times). Under most conditions, the error between the full model and the correlations is well below 7 %. Higher errors were observed for the pseudo steady state expression at high/ low states of charge where the assumption of uniform reaction distributions loses validity. Here, the short time ASI has higher error at low states of charge due to the nonlinearity of the open circuit voltage equation, which is assumed linear in the formulation of the simplified algebraic expression.

25 ENERGY STORAGE↗
DOE OSTI2023

High-Mass Loading of Flower-like Ni-MoS 2 microspheres Toward Efficient Intercalation pseudocapacitive Electrode

This work reports the exploration of intercalation pseudocapacitance in a thicker electrode of flowerlike Ni-doped MoS 2 microspheres that features a mass loading of ~10 mg/cm 2 without sacrificing the gravimetric capacitance (~425 F/g at 5 mV/s). Integration of Ni atoms into MoS 2 microspheres not only stabilized the structural integrity but also ameliorated the rapid intercalation and deintercalation of electrolyte ions even at a commercial-level mass loading. The energy instability by Ni doping significantly changed the local bonding behavior and the overall electronic structure of MoS 2 , facilitating the breaking of the MoS 2 layer and generation of more active edge sites, which are responsible for faster reaction kinetics. The experiments attribute the overall capacitance enhancement in (Mo-Ni)S 2 to the increased rate of electrolyte ion insertion and extraction, which is confirmed by b-values close to 0.5, at different potentials, indicating that the current response predominantly depends on the diffusive mechanism for both MoS 2 and Ni-MoS 2 thicker electrodes. The symmetric device constructed with Ni-MoS 2 microspheres exhibited a capacitance value of 101 F/g in 1 mV/s, for which the energy density is 9 Wh/kg, as well as attained an outstanding cycling stability of 10000 cycles with 60% retention at 2 A/g. In addition to providing insights into the development of 2D TMDs, this work explores the design of robust and highly efficient intercalation electrode material for electrochemical energy storage devices.

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

Revolutionizing Lithium Storage Capabilities in TiO 2 by Expanding the Redox Range

TiO 2 is a widely recognized intercalation anode material for lithium-ion batteries (LIBs), yet its practical capacity is kinetically constrained due to sluggish lithium-ion diffusion, leading to a lithiation number of less than 1.0 Li + (336 mAh g -1 ). Here, the growth of TiO 2 crystallites is restrained by integrating Si into the TiO 2 framework, thereby enhancing the charge transfer and creating additional active sites potentially residing at grain boundaries for Li + storage. This strategy is corroborated by the expanded redox range of Ti, as thoroughly demonstrated via synchrotron radiation-based X-ray spectroscopy and Cs-corrected electron microscopy. Consequently, when deployed for lithium storage, the tailored material achieves an extraordinarily high reversible capacity of 559 mAh g -1 , 116% of the theoretical maximum of 483 mAh g -1 calculated based on all active species, while simultaneously retaining superior rate capability and robust cycling stability. Further, this work offers fresh perspectives on the revitalization of traditional electrode materials to achieve enhanced capacities.

25 ENERGY STORAGE↗