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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 OSTI2022

Halide sublattice dynamics drive Li-ion transport in antiperovskites

Here, in this work, we resolve how proton dynamics and halide mixing enhance or impede ionic conduction in protonated lithium antiperovskites (pLiAP) at compositions near the eutectic points of the halide salts. As a material class, pLiAPs of the form Li 3-x OH x X, (X = Cl, Br) show vast compositional design freedom; however, the resulting properties are susceptible to synthesis and processing methodologies. Proton incorporation and halide mixing stabilize the perovskite cubic phase at low temperatures (<50 °C) and using halide mixtures near the eutectic points (~250 to 300 °C) offer possibilities of lower temperature and faster synthesis and processing conditions (<1 h). Mixed-halide compositions such as Li 2 OHCl 0.37 Br 0.63 lead to a 30-fold improvement in room temperature ionic conductivity of a single halide structure, 1.5 × 10 -6 vs. 4.9 × 10 -8 S cm -1 (Li 2 OHCl). We combine infrared spectroscopy and nuclear magnetic resonance with first-principles density functional theory calculations to deconvolute halide mixing effects from local proton dynamics on Li-ion transport. In contrast to what has been supposed, our findings suggest that the halide sublattice dynamics, besides the OH rotation, correlate strongly with the fast-ion conduction at high temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Single-atom vs. single-superatom as catalysts for ammonia production

A new class of single-superatom catalyst (TiO, ZrO, and WC) supported on graphene is shown to outperform the stability and activity of their corresponding single-atom catalysts (Ni, Pd and Pt) for the electrochemical nitrogen reduction reaction.

Kilic, Mehmet Emin [Physics Department, Virginia C↗
DOE OSTI2021

Binding of noble gas atoms by superhalogens

Because of their closed shells, noble gas (Ng) atoms (Ng = Ne, Ar, Kr, and Xe) seldom take part in chemical reactions, yet finding such mechanisms not only is of scientific interest but also has practical significance. Following a recent work by Mayer et al. [Proc. Natl. Acad. Sci. U. S. A. 116, 8167–8172 (2019)] on the room temperature binding of Ar to a superelectrophilic boron site embedded in a negative ion complex, B 12 (CN) 11 - , we have systematically studied the effect of cluster size and terminal ligands on the interaction of Ng by focusing on B 12 X 11 (Ng) (X = H, CN, and BO) and B 12 X 10 (Ng) 2 (X = CN and BO) whose stabilities are governed by the Wade–Mingos rule and on C 5 BX 5 (Ng) (X = H, F, and CN) and C 4 B 2 (CN) 4 (Ng) 2 whose stabilities are governed by the Huckel’s aromaticity rule. Our conclusion, based on density functional theory, is that both the cluster size and the terminal ligands matter—the interaction between the cluster and the Ng atoms becomes stronger with increasing cluster size and the electron affinity of the terminal ligands. Our studies also led to a counter-intuitive finding—removing multiple terminal ligands can enable electrophilic centers to bind multiple Ng atoms simultaneously without compromising their binding strength.

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

Observation of halogen-like behavior of gold in fluorinated bimetallic CoAuF 1-2 − and CuAuF 1-2 − clusters: Anion photoelectron spectroscopy and density functional theory

Using size-selected anion photoelectron spectroscopy and density functional theory, we investigated the structures and properties of fluorinated bimetallic clusters CoAuF 1-2 − and CuAuF 1-2 − and their neutrals. Both experimental and theoretical results show that in these cluster anions, Au behaves like a halogen atom. For example, the measured vertical detachment energies (VDEs) of CoAuF − (2.00 ± 0.08 eV) and CuAuF − (3.8 ± 0.1 eV) are close to those of CoF 2 − (2.12 ± 0.08 eV) and CuF 2 − (3.58 ± 0.08 eV), respectively. The theoretical results show that the geometries and electronic structures of CoAuF − and CuAuF − are similar to those of CoF 2 − and CuF 2 − . The natural population analysis and natural electron configuration analyses further confirm that the electronic properties of Au in MAuF − (M = Co, Cu) mimic those of MF 2 − . In addition, the electron localization function analyses show that the M-Au chemical bonds are similar to the corresponding M-F chemical bonds, providing evidence for the ionic nature of the interactions. When a second F atom is attached to the CoAuF − and CuAuF − clusters, the VDEs of the resulting CoAuF 2 − and CuAuF 2 − are 4.38 ± 0.08 eV and 3.71 ± 0.08 eV, respectively, indicating their superhalogen character as these values are higher than those of halogen anions. The results may be useful for understanding the properties of gold at the nanoscale that play an important role in catalysis and nanotechnology.

Ab-initio methods↗
DOE OSTI2022

Thermoelectric Figure of Merit of a Superatomic Crystal Re 6 Se 8 I 2 Monolayer

Superatomic materials are newly emerging candidates for high-performance thermoelectric (TE) devices due to their intrinsic ultralow thermal conductivities. However, the low TE power factor becomes a huge obstacle to reaching the required the dimensionless figure of merit (ZT) values for practical applications. Here, motivated by the recently synthesized superatomic Re 6 Se 8 I 2 monolayer [J. Am. Chem. Soc. 144, 74 (2022)], we study its superior thermoelectric properties by using density functional theory combined with phonon Boltzmann transport theory and deep potential molecular dynamics. We show that the large mass and anharmonic Re-I bonds introduce strong phonon scattering and result in low lattice thermal conductivity of 1.20 W m -1 K -1 at 300 K, while the strong and harmonic Re-Se network ensures the high TE power factor of 4344 μW m -1 K -2 in b direction for n-type doping. This is an order of magnitude higher than that of other cluster-based materials. Due to the low thermal conductivity and high TE power factor, Re 6 Se 8 I 2 exhibits high ZT values of 1.20 (500 K) and 1.43 (900 K) with n-type doping along the b direction among all the cluster-based thermoelectric materials reported so far.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Built-in electric field control of magnetic coupling in van der Waals semiconductors

Electrical control of magnetism in a two-dimensional (2D) semiconductor is of great interest for emerging nanoscale low-dissipation spintronic devices. Here, we propose a general approach of tuning magnetic coupling and anisotropy of a van der Waals (vdW) 2D magnetic semiconductor via a built-in electric field generated by the adsorption of superatomic ions. Using first-principles calculations, we predict a significant enhancement of ferromagnetic coupling and a great change of magnetic anisotropy in 2D semiconductors when they are sandwiched between superatomic cations and anions. The magnetic coupling is directly affected by the built-in electric field, which lifts the energy levels of mediated ligands' orbitals and enhances the superexchange interactions. Finally, these findings will be of interest for ionic gating controlled ferromagnets and magnetoelectronics based on vdW 2D semiconductors.

2-dimensional systems↗
DOE OSTI2022

Interfacial triferroicity in monolayer chromium dihalide

Couplings between different ferroics in two-dimensional (2D) materials, with atomic thickness and van der Waals surface, have been long sought but not yet realized. We show the first-principles evidence of unique triferroic couplings in recently synthesized CrI 2 monolayer. Its ferroelasticity with a low switching barrier stems from the Jahn-Teller effect. When coupled with the interaction of a substrate, a type of interfacial ferroelectricity with direction determined by the ferroelastic states can emerge which can be switched following the same low-barrier pathway of ferroelastic switching. The direction of its striped antiferromagnetism is also governed by its ferroelastic states, leading to a coupling of ferroelasticity, ferroelectricity, and magnetism. Such mechanism of multiferroic couplings, denoted as interfacial Jahn-Teller triferroicity, can be applied to other 2D materials such as CuC l2 and their Janus monolayers, enabling electrical manipulation of spintronics for efficient nonvolatile random-access memories.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Symmetry-driven persistent spin texture for the two-dimensional nonsymmorphic CdTe and ZnTe crystal structures

In this paper, two nonsymmorphic two-dimensional structures of CdTe and ZnTe are modeled, and using state-of-the-art density functional theory with the group theory of solids, their symmetry-enforced electronic properties are studied. The in-plane ferroelectricity coupled with strong spin-orbit coupling induces a unidirectional out-of-plane Rashba spin-orbit field that can host a momentum-independent uniform spin configuration known as persistent spin texture (PST) at the Brillouin zone center. PST in these structures is found to be robust against external perturbations such as strain, structural distortion, and independent of layer thickness. These unprecedented intrinsic spin transport properties hold utmost importance in spintronics, as the experimental stringent condition of equal Rashba and Dresselhaus constants [Phys. Rev. Lett. 90, 146801 (2003)] is eliminated. The calculated persistent spin helix wavelength of <~5 nm paves the way for developing next-generation nanosized nonballistic spin field-effect transistors compared with micrometer-sized GaAs/AlGaAs quantum wells. Further, these materials exhibit finite spin Hall conductivity at the band edges and hence can be used in ferromagnet-free spin Hall transistors. Although CdTe and ZnTe systems have been widely studied for photocatalysis and solar cell applications over the past few decades, their potential application in spintronic devices has not been explored. Mono/few layers of CdTe and ZnTe synthesized from (110) facets of bulk zinc-blende crystals [Nat. Commun. 3, 1057 (2012)] satisfy all symmetry operations of the nonsymmorphic space group and hence can be considered ideal materials to verify our theoretical results experimentally.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Electrical Control of Magnetic Phase Transition in a Type-I Multiferroic Double-Metal Trihalide Monolayer

Controlling magnetism of two-dimensional multiferroics by an external electric field provides special opportunities for both fundamental research and future development of low-cost electronic nanodevices. Here, we report a general scheme for realizing a magnetic phase transition in 2D type-I multiferroic systems through the reversal of ferroelectric polarization. First, based on first-principles calculations, we demonstrate that a single-phase 2D multiferroic, namely, ReWCl 6 monolayer, exhibits two different low-symmetric ($C_2$) phases with opposite in-plane electric polarization and different magnetic order. As a result, an antiferromagnetic-to-ferromagnetic phase transition can be realized by reversing the in-plane electric polarization through the application of an external electric field. These findings not only enrich the 2D multiferroic family, but also uncover a unique and general mechanism to control magnetism by electric field, thus stimulating experimental interest.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Metallic and ferromagnetic carbon allotrope discovered using molecular precursors

Although carbon materials are known for their versatile structures and properties, a crystalline phase of carbon being both metallic and ferromagnetic is yet to be found. Here, using an organic molecular precursor 3,3-dimethyl-1-butene ( C 6 H 12 ) and a comprehensive theoretical study, we have discovered a metastable crystalline carbon phase that is both metallic and ferromagnetic under ambient conditions. The new carbon structures, produced by stacking puckered layers of 4,6-membered rings, are found to exhibit exotic electronic, magnetic, and mechanical properties originating from a special s p 2 − s p 3 bonding topology. These findings open the prospect of realizing the metallic and ferromagnetic carbon allotrope in practice. Published by the American Physical Society 2025

Fang, Hong (ORCID:0000000209688687)↗
DOE OSTI2023

Kinetic Effects of Anion Clusters on the Interfacial Stability between Solid-State Electrolyte and Metal Anode

The success of all-solid-state batteries (ASSBs) depends on the solid-state electrolyte (SSE) exhibiting high interfacial stability and room-temperature ionic conductivity. However, the current SSEs, especially those with practical ionic conductivities (≥10 –3 S/cm) at room temperature, often develop unstable interfaces at the metal anode, in some cases with even greater severity than with liquid organic electrolytes. Despite persistent efforts, achieving interfacial stability and sufficient ionic conductivity simultaneously represents one of the greatest challenges in ASSBs. The current approaches focus on stabilizing the interface by incorporating secondary interlayers or introducing coatings by surface engineering. The method is often material-specific, and the added interlayers often deteriorate during cycling. In this work, using phase analysis and explicit interface modeling, we demonstrate a strategy to kinetically stabilize the interface between the SSE and metal anode by incorporating selected monoanion clusters in the SSE; they can effectively lower or even halt the reduction kinetics at the interface by promoting on-site formation of interphases that are highly electron insulating. The study provides insight into the kinetic effects to achieve SSEs with superior properties in bulk and at the interface.

25 ENERGY STORAGE↗
DOE OSTI2023

First Principles Modeling of Cluster-Based Solid Electrolytes (Final Technical Report)

Given the trend of global warming and the urgent need to transition from fossil fuels to green energy, lithium-ion batteries continue to be an integral part of our lives. Design, development, and understanding of novel solid-state electrolyte materials play the key role for achieving next-generation all-solid-state batteries with high energy and great safety. The current modeling schemes to develop advanced solid electrolytes are focusing on materials in which the building blocks are individual atoms. Our theoretical approach is a paradigm shift in solid-state electrolyte design. Instead of atoms, we focus on clusters as the building blocks and model these solid electrolytes and their interfaces with electrodes, especially Li-metal anode, for their successful implementation in solid-state batteries. The advantage of using the cluster ions to replace elemental ions is that the size, composition, and shape of the former can be tailored to achieve higher ionic conductivity at room temperature, electrochemical stability, and charge transfer across solid-solid interfaces than conventional materials. Specifically, the project includes: (1) Developing cluster-based solid electrolytes, where the halogen components are replaced by cluster ions that mimic the chemistry of halogens but are characterized by additional degrees of freedom, including the size, shape, composition, and motional dynamics under excitation. (2) Providing a fundamental understanding of the ion conduction mechanism in the developed cluster-based solid electrolytes; (3) Modeling the interfacial properties (i.e., structural, chemical, and transport properties) between the cluster-based solid electrolytes and electrodes at the atomic level. For the cluster-based solid electrolytes incompatible with the Li-metal anode or cathode materials, potential candidates for interfacial coatings are identified and studied. (4) Providing a theoretical framework towards optimizing critical parameters of the solid-state electrolytes that guides experimentalists to attain desired cathode-electrode interface for cluster-based solid-state electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2023

Effects of Anion Clusters at Solid-State Electrolyte and Electrode Interfaces

Stability and transport properties at the electrolyte-electrode interface are of great importance to the performance of all-solid-state batteries with solid-state electrolytes (SSEs). Most recent studies have shown that mono-/poly-anion clusters that are either original contained or doped in the SSE can lead to intriguing (transport, electronic, and mechanical) properties [1-6]. However, the effects of anion clusters on the SSE-electrode interfaces are unknown. Here, we will investigate such effects and unravel the working mechanisms using phase/reactivity analysis and explicit interface modeling.

Fang, Hong↗