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Results for “Entropy stability”

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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Thin film growth effects on electrical conductivity in entropy stabilized oxides

Entropy stabilization has garnered significant attention as a new approach to designing novel materials. Much of the work in this area has focused on bulk ceramic processing, leaving entropy-stabilized thin films relatively under-explored. Following an extensive multi-variable investigation of polycrystalline (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 )O thin films deposited via pulsed laser deposition (PLD), it is shown here that substrate temperature and deposition pressure have strong and repeatable effects on film texture and lattice parameter. Further analysis shows that films deposited at lower temperatures and under lower oxygen chamber pressure are 40x less electrically resistive than otherwise identical films grown at higher temperature and pressure. Annealing these films in an oxygen-rich environment increases their electrical resistivity to match that of the films grown at higher temperatures and pressures. Because of this, the electric conductivity is hypothesized to be the result of polaron hopping mediated by transition metal valence changes which compensate for oxygen off-stoichiometry.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Semiconducting High-Entropy Chalcogenide Alloys with Ambi-ionic Entropy Stabilization and Ambipolar Doping

Entropy stabilization is a novel materials-design paradigm to realize new compounds with widely tunable properties. However, almost all entropy-stabilized materials so far are either conducting metals or insulating ceramics, with a clear dearth in the semiconducting regime. Here, a new class of the multi-cationic and -anionic entropy-stabilized chalcogenide alloys based on the (Ge,Sn,Pb)(S,Se,Te) formula are synthesized and characterized experimentally. The con-figurational entropy from the disorder of both the anion and the cation sublattices reaches a record value of ~2.2 R mol -1 for the equimolar composition and stabilizes the single-phase solid solution. Theoretical calculations and experiments both show that the synthesized alloys are thermodynamically stable at the growth temperature and kinetically metastable at room temperature, segregating by spinodal decomposition at moderate temperatures. In conclusion, doping and electronic transport measurements verify that the synthesized materials are ambipolarly dopable semiconductors, which paves the way for the wider adoption of entropy-stabilized chalcogenide alloys in functional applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Hidden transformations in entropy-stabilized oxides

We report entropy-stabilized oxides (ESO) display a reversible entropy-driven phase transformation that can be leveraged to produce a continuum of metastable phase states, allowing for property optimization and novel functionalities. X-ray absorption spectroscopy reveals that entropic stabilization extends to the electronic structure (valence state and cation coordination) in sintered (Co,Cu,Mg,Ni,Zn)O, manifesting as a tunable lattice distortion in the entropy-stabilized phase. Co, Cu, and Zn ions reversibly transform from six-fold to four-fold coordinated structures and from low to high valence states due to the competition between electronic structures that are equilibrium and enthalpy-driven or metastable and entropy-driven. The segregation of a Cu-rich tenorite phase and a Co-rich spinel phase influences the electronic structure evolution. ESOs can adjust their electronic structures through heat treatment, providing a powerful tool for developing functional properties. These results indicate that the definition of entropy stabilization should include entropy-stabilized electronic structures, providing motivation to reassess previously studied HEO materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

On the elastic anisotropy of the entropy-stabilized oxide (Mg, Co, Ni, Cu, Zn)O compound

Herein, we study the elastic properties of the entropy-stabilized oxide (Mg, Co, Ni, Cu, Zn)O using experimental and first principles techniques. Our measurements of the indentation modulus on grains with a wide range of crystallographic orientations of the entropy-stabilized oxide revealed a high degree of elastic isotropy at ambient conditions. First principles calculations predict mild elastic anisotropy for the paramagnetic structure, which decreases when the system is considered to be non-magnetic. When the antiferromagnetic state of CoO, CuO, and NiO is accounted for in the calculations, a slight increase in elastic anisotropy is observed, suggesting a coupling between magnetic ordering and the orientation dependent elastic properties. Furthermore, an examination of the local structure reveals that the isotropy is favored through local ionic distortions of Cu and Zn—due to their tendencies to form tenorite and wurtzite phases. The relationships between the elastic properties of the multicomponent oxide and those of its constituent binary oxides are reviewed. These insights open up new avenues for controlling isotropy for technological applications through tuning composition and structure in the entropy-stabilized oxide or the high-entropy compounds in general.

Entropy↗
DOE OSTI2021

Analysis of the SBP-SAT Stabilization for Finite Element Methods Part II: Entropy Stability

In the hyperbolic research community, there exists the strong belief that a continuous Galerkin scheme is notoriously unstable and additional stabilization terms have to be added to guarantee stability. In the first part of the series, the application of simultaneous approximation terms for linear problems is investigated where the boundary conditions are imposed weakly. By applying this technique, the authors demonstrate that a pure continuous Galerkin scheme is indeed linearly stable if the boundary conditions are imposed in the correct way. In this work, we extend this investigation to the nonlinear case and focus on entropy conservation. Here, by switching to entropy variables, we provide an estimation of the boundary operators also for nonlinear problems, that guarantee conservation. In numerical simulations, we verify our theoretical analysis.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2020

Entropy-stabilized single-atom Pd catalysts via high-entropy fluorite oxide supports

Single-atom catalysts (SACs) have attracted considerable attention in the catalysis community. However, fabricating intrinsically stable SACs on traditional supports (N-doped carbon, metal oxides, etc.) remains a formidable challenge, especially under high-temperature conditions. Here, we report a novel entropy-driven strategy to stabilize Pd single-atom on the high-entropy fluorite oxides (CeZrHfTiLa)O x (HEFO) as the support by a combination of mechanical milling with calcination at 900 °C. Characterization results reveal that single Pd atoms are incorporated into HEFO (Pd1@HEFO) sublattice by forming stable Pd–O–M bonds (M = Ce/Zr/La). Compared to the traditional support stabilized catalysts such as Pd@CeO 2 , Pd 1 @HEFO affords the improved reducibility of lattice oxygen and the existence of stable Pd–O–M species, thus exhibiting not only higher low-temperature CO oxidation activity but also outstanding resistance to thermal and hydrothermal degradation. This work therefore exemplifies the superiority of high-entropy materials for the preparation of SACs.

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

Densification of the entropy stabilized oxide (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 )O

The first entropy-stabilized oxide, (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 )O, was reported in 2015. Initial studies synthesized this material using solid state processing and were limited to densities < 80%. Here, we report a straightforward solid state route to sinter samples to densities up to 98% of the theoretical by identifying the role of oxygen and promoting the resulting mechanisms in densification. Previous works have studied effects of cation stoichiometry on the entropy-driven reaction to form a single phase, but few have explored the associated effects of anion stoichiometry and/or redox chemistry on both phase stability and densification. We demonstrate here that tuning heating rate and pO 2 during heating of initially-homogeneous calcined powders can enhance densifying diffusion processes and enable reliable sintering of dense (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 )O samples.

MATERIALS SCIENCE↗
DOE OSTI2020

Spin dynamics and a nearly continuous magnetic phase transition in an entropy-stabilized oxide antiferromagnet

In this work, the magnetic order and the spin dynamics in the antiferromagnetic entropy-stabilized oxide (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 )O (MgO-ESO) have been studied using muon spin relaxation (μSR) and inelastic neutron scattering. We find that antiferromagnetic order develops gradually in the sample volume as it is cooled below 140 K, becoming fully ordered around 100 K. The spin dynamics show a critical slowing down in the vicinity of the transition, and the magnetic order parameter grows continuously in the ordered state. These results indicate that the antiferromagnetic transition is continuous but proceeds with a Gaussian distribution of ordering temperatures. Additionally, the magnetic contribution to the specific heat determined from inelastic neutron scattering likewise shows a broad feature centered around 120 K. High-resolution inelastic neutron scattering further reveals an initially gapped spectrum at low temperature which sees an increase in a quasielastic contribution upon heating until the ordering temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2022

The role of Co valence in charge transport in the entropy‐stabilized oxide (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 )O

Abstract Many of the studies on the entropy‐stabilized oxide (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 )O have been heavily application‐based. Previous works have studied effects of cation stoichiometry on the entropy‐driven reaction to form a single phase, but a fundamental exploration of the effects of anion stoichiometry and/or redox chemistry on electrical properties is lacking. Using near‐edge X‐ray absorption fine structure (NEXAFS) and electrical measurements, we show that oxidizing thin film samples of (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 )O affects primarily the valence of Co, leaving the other cations in this high‐entropy system unchanged. This oxidation increases electrical conduction in these thin films, which occurs via small polaron hopping mediated by the Co valence shift from 2+ to a mixed 2+/3+ state. In parallel, we show that bulk samples sintered in an oxygen‐rich atmosphere have a lower activation energy for electrical conduction than those equilibrated in a nitrogen (reducing) atmosphere. Combining feasible defect compensation scenarios with electrical impedance measurements and NEXAFS data, we propose a self‐consistent interpretation of Co redox‐mediated small polaron conduction as the dominant method of charge transfer in this system.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Entropy-Stabilized Multication Fluorides as a Conversion-Type Cathode for Li-Ion Batteries–Impact of Element Selection

Metal fluorides (e.g., FeF 2 and FeF 3 ) have received attention as conversion-type cathode materials for Li-ion batteries due to their higher theoretical capacity compared to that of common intercalation materials. However, their practical use has been hindered by low round-trip efficiency, voltage hysteresis, and capacity fading. Cation substitution has been proposed to address these challenges, and recent advancements in battery performance involve the introduction of entropy stabilization in an attempt to facilitate reversible conversion reactions by increasing configurational entropy. Building on this concept, high entropy fluorides with five cations were synthesized by using a simple mechanochemical route. In order to examine the impact of element selection, Co 0.2 Cu 0.2 Ni 0.2 Zn 0.2 Fe 0.2 F 2 (HEF-Fe) was compared with Co 0.2 Cu 0.2 Ni 0.2 Zn 0.2 Mg 0.2 F 2 (HEF-Mg), replacing electrochemically inactive Mg with Fe as an active participant in the conversion reaction. Combining electrochemical measurements with first-principles calculations, high-resolution electron microscopy, and synchrotron X-ray analysis, HEFs’ battery performances and conversion reaction mechanisms were investigated in detail. The results highlighted that replacement of Mg with Fe was beneficial, with enhanced capacity, rate capability, and surface stability. In addition, it was found that HEF-Fe showed similar cycle stability without an electrochemically inactive element. In conclusion, these findings provide valuable insights for the design of high entropy multielement fluorides for improved Li-ion battery performance.

25 ENERGY STORAGE↗
DOE OSTI2022

Effects of local compositional and structural disorder on vacancy formation in entropy-stabilized oxides from first-principles

Entropic stabilization has evolved into a strategy to create new oxide materials and realize novel functional properties engineered through the alloy composition. Achieving an atomistic understanding of these properties to enable their design, however, has been challenging due to the local compositional and structural disorder that underlies their fundamental structure-property relationships. Here, we combine high-throughput atomistic calculations and linear regression algorithms to investigate the role of local configurational and structural disorder on the thermodynamics of vacancy formation in (MgCoNiCuZn)O-based entropy-stabilized oxides (ESOs) and their influence on the electrical properties. We find that the cation-vacancy formation energies decrease with increasing local tensile strain caused by the deviation of the bond lengths in ESOs from the equilibrium bond length in the binary oxides. The oxygen-vacancy formation strongly depends on structural distortions associated with the local configuration of chemical species. Vacancies in ESOs exhibit deep thermodynamic transition levels that inhibit electrical conduction. By applying the charge-neutrality condition, we determine that the equilibrium concentrations of both oxygen and cation vacancies increase with increasing Cu mole fraction. Our results demonstrate that tuning the local chemistry and associated structural distortions by varying alloy composition acts an engineering principle that enables controlled defect formation in multi-component alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Bayesian optimization of entropy-stabilized metal fluoride conversion cathodes and their synthesis

Fluoride-based conversion cathodes are promising for next-generation Li ion batteries because of their high voltage and energy densities. High entropy earth abundant fluoride cathodes are attractive for sustainable battery because of the potentially higher cycling stability. While Ni and Co containing equimolar alloys stabilized by high entropy were considered previously, Ni and Co free non-equimolar metal alloy compositions might offer new opportunities to increase materials stability and average voltage. This opportunity was pursued using Bayesian optimization of average voltage for the computational prediction of (Fe x1 Cu x2 Zn x3 Mn x4 Mg x5 )F 2 cathode chemistries. Theoretical voltage, room temperature free energy, and electronic structure of potentially high voltage compositions were computed using density functional theory calculations. Here, the experimental realization of non-equimolar quinary Co and Ni free fluorides with stable rutile single phase and improved conversion reaction voltage by up to 28 % compared to the equimolar alloy demonstrated the power of Bayesian optimization methods for the computationally guided experimental synthesis of fluoride cathodes. Finally, non-equimolar cathode chemistries were found with cycling stability superior to known multi-element fluorides.

25 ENERGY STORAGE↗
DOE OSTI2022

Entropy Stabilization Effects and Ion Migration in 3D “Hollow” Halide Perovskites

A recently discovered new family of 3D halide perovskites with the general formula (A) 1–x (en) x (Pb) 1–0.7x (X) 3–0.4x (A = MA, FA; X = Br, I; MA = methylammonium, FA = formamidinium, en = ethylenediammonium) is referred to as “hollow” perovskites owing to extensive Pb and X vacancies created on incorporation of en cations in the 3D network. The “hollow” motif allows fine tuning of optical, electronic, and transport properties and bestowing good environmental stability proportional to en loading. To shed light on the origin of the apparent stability of these materials, we performed detailed thermochemical studies, using room temperature solution calorimetry combined with density functional theory simulations on three different families of “hollow” perovskites namely en/FAPbI 3 , en/MAPbI 3 , and en/FAPbBr 3 . We found that the bromide perovskites are more energetically stable compared to iodide perovskites in the FA-based hollow compounds, as shown by the measured enthalpies of formation and the calculated formation energies. The least stable FAPbI 3 gains stability on incorporation of the en cation, whereas FAPbBr 3 becomes less stable with en loading. This behavior is attributed to the difference in the 3D cage size in the bromide and iodide perovskites. Configurational entropy, which arises from randomly distributed cation and anion vacancies, plays a significant role in stabilizing these “hollow” perovskite structures despite small differences in their formation enthalpies. With the increased vacancy defect population, we have also examined halide ion migration in the FA-based “hollow” perovskites and found that the migration energy barriers become smaller with the increasing en content.

36 MATERIALS SCIENCE↗