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At least 37 records · Page 2

Ultrafast Photoflash Synthesis of High-Entropy Oxide Nanoparticles

High-entropy metal oxides (HEOs) have recently received growing attention for broad energy conversion and storage applications due to their tunable properties. HEOs typically involve the combination of multiple metal cations in a single oxide lattice, thus bringing distinctive structures, controllable elemental composition, and tunable functional properties. Many synthesis methods for HEOs have been reported, such as solid-state reactions and carbon thermal shock methods. These methods frequently are energy-intensive or require relatively expensive heating equipment. In this work, we report an ultrafast photoflash synthesis method for HEO nanoparticles on diverse substrates. The energy input is provided by a commercial Xe photoflash unit, which triggers exothermic reactions to convert metal salt precursors to HEO nanoparticles within tens of milliseconds. The formation of HEO nanoparticles is attributed to the ultrafast heating (∼106 K/s) and cooling (∼105 K/s) rates of the photoflash and overall high temperature (>1000 K) during the ultrafast synthesis process. When the synthesized CoNiFeCrMn oxide (HEO) is tested as an oxygen evolution reaction electrocatalyst, it shows similar activity to similar materials prepared by other methods. We believe this photoflash synthesis provides a simple method for many others to synthesize diverse HEOs and explore their properties and potential applications.

exothermic reaction synthesis↗

Manganese-rich high entropy oxides for lithium-ion batteries:materials design approaches to address voltage fade

Lithium- and manganese-rich oxides are of interest as lithium-ion battery cathode materials as Mn is earth abundant, low cost, and can deliver high capacity. Herein, a high entropy strategy was used to prepare Mn rich high entropy oxide (HEO) materials by including four additional metals (Ni, Co, Fe and Al) in the compositions using a mild co-precipitation method. Two HEOs (Li x Ni 0.1 Mn 0.6 Co 0.1 Al 0.1 Fe 0.1 O y , where x = 1.5 for HEO-L and x = 0.5 for HEO-H) with layered and spinel-layered hybrid structures were investigated where the morphology, elemental composition, structure, atomic level phase distribution, and electrochemistry were determined. The HEO-L samples involve a Li 2 TMO 3 layered structure with ~39% stacking faults. HEO-H is a hybrid structure comprised of 80 wt% spinel and 20 wt% LiMO 2 layered structure. The high entropy manganese-rich HEO-L showed higher capacity and 93% retention of the average voltage after 100 cycles while HEO-H showed higher capacity retention and near 100% average voltage retention. Finally, operando X-ray absorption spectroscopy revealed that the Ni, Co, and Mn are redox active in both materials while the Fe center remains at the Fe 3+ oxidation state throughout cycling, where the changes in the oxidation states for both materials during discharge were consistent with the delivered electrochemical capacity rationalizing the observed electrochemistry.

25 ENERGY STORAGE↗

(Mg,Mn,Fe,Co,Ni)O: A rocksalt high-entropy oxide containing divalent Mn and Fe

High-entropy oxides (HEOs) have aroused growing interest due to fundamental questions relating to their structure formation, phase stability, and the interplay between configurational disorder and physical and chemical properties. Introducing Fe(ιι) and Mn(ιι) into a rocksalt HEO is considered challenging, as theoretical analysis suggests that they are unstable in this structure under ambient conditions. Here, we develop a bottom-up method for synthesizing Mn- and Fe-containing rocksalt HEO (FeO-HEO). We present a comprehensive investigation of its crystal structure and the random cation-site occupancy. We show the improved structural robustness of this FeO-HEO and verify the viability of an oxygen sublattice as a buffer layer. Compositional analysis reveals the valence and spin state of the iron species. We further report the antiferromagnetic order of this FeO-HEO below the transition temperature ~218 K and predict the conditions of phase stability of Mn- and Fe-containing HEOs. Our results provide fresh insights into the design and property tailoring of emerging classes of HEOs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Human Mars Mission: SEP Architecture Crew Taxi Propulsion Stage Study and Design and Technology for Reaction and Control System

The Mars exploration is a candidate pathway to expand human presence and useful activities in the solar system. There are several propulsion system options being considered to place the Mars payload on its inter-planetary transfer trajectory. One propulsion option is the use of Solar Electric Propulsion (SEP) to spiral out with the Mars payload from an initial Low Earth Orbit (LEO) to an elliptical High Earth Orbit (HEO). This report, presented in annotated facing page format, describes the work completed on the design of a crew taxi propulsion stage used in conjunction with the SEP. Transportation system/mission analysis topics covered in this report include sub-system analysis, trajectory profile description, mass performance and crew taxi stage sizing, stage configuration, stage cost, and Trans-Mars Injection (TMI) launch window. The high efficiency of SEP is used to provide the major part of the TMI propulsion maneuver. Orbital energy is continuously added over a period of approximately twelve months. The SEP and Mars payload follow a spiral trajectory from an initial LEO to a final elliptical HEO. A small chemical stage is then used to provide the final part of the TMI. The now unloaded SEP returns to LEO to repeat another spiral trajectory with payload to HEO. The spiral phase of the SEP's trajectory takes several months to reach HEO, thus significantly increasing the exposure time of the crew to zero-gravity. In order to minimize the long zero-gravity effects, a high thrust chemical stage delivers the crew to the SEP's HEO. The crew rendezvous with the Mars payload in HEO. After a checkout period the Mars payload with the crew is injected onto a Trans-Mars Trajectory by a small chemical stage.

Young, Archie↗

Human Mars Mission: SEP Architecture, Crew Taxi Propulsion Stage Study and Design and Technology for Reaction and Control System

The Mars exploration is a candidate pathway to expand human presence and useful activities in the solar system. There are several propulsion system options being considered to place the Mars payload on its interplanetary transfer trajectory. One propulsion option is the use of Solar Electric Propulsion (SEP) to spiral out with the Mars payload from an initial Low Earth Orbit (LEO) to an elliptical High Earth Orbit (HEO). This report, presented in annotated facing page format, describes the work completed on the design of a crew taxi propulsion stage used in conjunction with the SEP. Transportation system/mission analysis topics covered in this report include sub-system analysis, trajectory profile description, mass performance and crew taxi stage sizing, stage configuration, stage cost, and Trans-Mars Injection (TMI) launch window. The high efficiency of SEP is used to provide the major part of the TMI propulsion maneuver. Orbital energy is continuously added over a period of approximately twelve months. The SEP and Mars payload follow a spiral trajectory from an initial LEO to a final elliptical HEO. A small chemical stage is then used to provide the final part of the TMI. The now unloaded SEP returns to LEO to repeat another spiral trajectory with payload to HEO. The spiral phase of the SEP's trajectory takes several months to reach HEO, thus significantly increasing the exposure time of the crew to zero-gravity. In order to minimize the long zero-gravity effects, a high thrust chemical stage delivers the crew to the SEP's HEO. The crew rendezvous with the Mars payload in HEO. After a checkout period the Mars payload with the crew is injected onto a Trans-Mars Trajectory by a small chemical stage.

Young, Archie↗

In Situ Cyclized Polyacrylonitrile Coating: Key to Stabilizing Porous High-Entropy Oxide Anodes for High-Performance Lithium-Ion Batteries

High-entropy oxides (HEOs) composed of multiple metal elements have attracted great attention as anode materials for lithium-ion batteries (LIBs) due to the synergistic effects of various metal species. However, the practical applications of HEOs are still plagued by poor conductivity, unstable solid electrolyte interphase (SEI) and poor cycling stability. In this work, nanosized (FeCoNiCrMn) 3 O 4 HEO (NHEO) is prepared successfully by the NaCl-assisted mechanical ball-milling strategy. Novelly, polyacrylonitrile (PAN) is used as the binder and then in situ thermochemically cyclized to construct a cyclized PAN (cPAN) outer layer onto NHEO (NHEO-cPAN). The in situ formed cPAN coating not only improves the electrical conductivity, but also reinforces the structural and interfacial stability, and thereby, the resulted NHEO-cPAN electrode exhibits significantly enhanced rate and cyclic performance. Specifically, NHEO-PAN500 electrode delivers a high reversible capacity of 560 mAh g –1 at 5 A g –1 and a high-capacity retention of 83% over 800 cycles at 3 A g –1 . Furthermore, the structural evolution and electrochemical behavior of NHEO-PAN electrode during discharge/charge is systematically investigated by operando X-ray diffraction, in situ impedance spectroscopy and ex situ high-resolution transmission electron microscopy. Therefore, this work provides new insights into the engineering of electrode and interphase for high-performance HEO electrode materials, potentially enlightening the practical applications of HEO-based LIBs.

25 ENERGY STORAGE↗

Synthesis and Lithium Storage Properties of Spinel (Al 0.2 Mn 0.2 Co 0.2 Ni 0.2 Zn 0.2 ) 3 O 4 High-Entropy Oxide

High-entropy oxides (HEOs) have garnered significant interest as next-generation anode materials for lithium-ion batteries (LIBs) due to their high theoretical specific capacity and excellent structural stability. This study successfully synthesized spinel-structured (Al 0.2 Mn 0.2 Co 0.2 Ni 0.2 Zn 0.2 ) 3 O 4 HEO via a sol–gel method. The material was characterized by XRD, Raman and TEM, confirming a homogeneous single-phase spinel structure, with uniformly distributed elements-a hallmark of HEOs. Electrochemical tests demonstrated a stable cycling performance (438 mAh g −1 at 100 mA g −1 after 100 cycles and 350 mAh g −1 at 1 A g −1 after 1000 cycles) and rate capacity of 159 mAh g −1 at 2 A g −1 , The remarkable long-term cyclability and good rate capability highlight the potential of this HEO for practical applications in durable, high-power lithium-ion batteries. This work underscores the advantage of incorporating structurally stabilizing elements in HEOs for advanced energy storage.

anode materials↗

Zero-strain high entropy spinel oxide (FeNiCuCrMn) 3 O 4 @rGO as high-performance anode for sodium ion battery

High entropy spinel oxides (HEOs), as a new type of anode material with at least five transition metal elements and high theoretical specific capacity, have enormous promise in sodium ion batteries (SIBs). However, the influence of different transition metal elements on the structure and electrochemical performances of HEOs is not clear. Here, in this study, the addition of Mn to HEO can increase the surface oxygen vacancy (O v ) concentration, shorten the band gap, and enhance the electrochemical performance of (FeNiCuCrMn) 3 O 4 @rGO. XPS results show (FeNiCuCrMn)3O4@rGO has the highest surface O v concentration. Ab initio calculations demonstrate that the indirect band gap of (FeNiCuCrMn)3O4@rGO is 0.068 eV. In situ X-ray diffraction and synchrotron X-ray absorption spectroscopy reveal that (FeNiCuCrMn) 3 O 4 @rGO exhibits a zero-strain characteristic with an inconsequential unit cell volume change of 0.2 %. Specifically, (FeNiCuCrMn) 3 O 4 @rGO as anode materials for SIBs show good cyclic stability (with a capacity retention of 84 % at 500 mA g −1 after 3000 cycles). Overall, this work provides a new direction for optimizing transition metal elements in HEOs.

36 MATERIALS SCIENCE↗

Interface-engineered (CrMnTiZnCo) 3 O 4 @polypyrrole nano-hybrids for superior lithium storage

High-entropy oxides (HEO) have emerged as promising anode materials for lithium-ion batteries (LIBs) due to their high theoretical specific capacity. However, their practical application is hindered by several challenges, including significant volume expansion, electrode pulverization, and substantial irreversible capacity loss during initial cycles. To address these limitations, this study designed a novel core-shell composite material, denoted as HEO@PPy, which consists of a (CrMnTiZnCo) 3 O 4 -based HEO core and a polypyrrole (PPy) shell. This composite demonstrates remarkable electrochemical performance: it maintains a specific capacity of 1090.1 mAh/g after 100 cycles at 100 mA/g and retains 521.8 mAh/g after 1000 cycles at 1 A/g, highlighting its superior cycling stability. Furthermore, it exhibits excellent rate capability, delivering a capacity of 372.1 mAh/g even at a high current density of 5 A/g. These findings confirm that the strategic compositional and structural design of HEOs, combined with hybridization with conductive polymers like PPy, provides a viable pathway for developing advanced anode materials for next-generation, high-performance lithium-ion batteries.

25 ENERGY STORAGE↗

Effect of crystallite size on lithium storage performance of high entropy oxide (Cr 0.2 Mn 0.2 Co 0.2 Ni 0.2 Zn 0.2 ) 3 O 4 nanoparticles

High-entropy oxides (HEOs), known for their high theoretical capacity and structural stability, are considered promising anode materials for next-generation lithium-ion batteries (LIBs). In this research, we synthesized a novel spinel-type HEO, (Cr 0.2 Mn 0.2 Co 0.2 Ni 0.2 Zn 0.2 ) 3 O 4 , using a solution combustion method. By adjusting the quantity of the combustion agent, we produced samples with varying crystallite sizes. The crystallite size of the HEOs initially enlarges with an increased combustion agent, then diminishes. The enhancement of crystallite size correlates with improved electrochemical performance for lithium storage. Notably, the (Cr 0.2 Mn 0.2 Co 0.2 Ni 0.2 Zn 0.2 ) 3 O 4 nanoparticles, with the largest crystallite size of 36.3 nm, demonstrated a reversible capacity of 343 mA h g -1 after 100 cycles at 100 mA g -1 , a capacity retention to 319 mA h g -1 after 1000 cycles at 1 A g -1 , and a commendable rate capability of 260 mA h g -1 at 2 A g -1 . Furthermore, this study underscores the pivotal role of crystallite size in LIB performance and presents a viable strategy to enhance the lithium storage capabilities of HEOs and other metal oxides.

25 ENERGY STORAGE↗

(CrMnCoNiZn) 3 O 4 @PPy core-shell nanocomposite with excellent electrochemical performance as lithium-ion battery anode

High entropy oxides (HEOs) have an excellent potential for use as electrode materials in lithium-ion batteries (LIBs) due to their high theoretical specific capacity. In this work, spinel-structured (CrMnCoNiZn) 3 O 4 HEO nanoparticles with five elements in equal molar ratio is first generated by solution combustion method. (CrMnCoNiZn) 3 O 4 @polypyrrole (PPy) nanocomposites are prepared by in-situ polymerization method. As an anode for lithium-ion batteries, the electrochemical performance of the (CrMnCoNiZn) 3 O 4 @PPy composite outperforms that of (CrMnCoNiZn) 3 O 4 nanoparticles. The capacity is 802 mAh/g after 100 cycles at a current density of 100 mA/g, 416 mAh/g after 1000 cycles at a high current density of 1 A/g, and 360 mAh/g rate capacity at 2 A/g. The excellent electrochemical performance of the composites is mainly due to the fact that the conductive and flexible PPy is encapsulated on the high-entropy oxides, which can alleviate the volume change triggered by extraction-insertion of lithium ions process, as well as enhance the electrical conductivity and reduce the occurrence of some side reactions. Finally, this method of compositing materials can also be used in other HEOs and conductive polymers, providing a new idea to enhance the electrochemical properties of HEOs.

25 ENERGY STORAGE↗

Preparation and electrochemical properties of high-entropy oxide Li x (CrMnCoNiZn) 3-x O 4

High-entropy oxides (HEOs) have gained significant attention as anode materials for lithium-ion batteries (LIBs) due to their high theoretical specific capacity, synergistic effects of constituent elements, and enhanced structural stability induced by high entropy. Here, this study investigates the electrochemical properties of a novel series of HEOs, Li x (CrMnCoNiZn) 3-x O 4 , synthesized via the sol-gel method. As lithium content increases, the electrochemical lithium storage performance of the HEOs improves, attributed to the rise in high-valence states and oxygen vacancies. The high valence state of elements facilitates greater electron transfer, enhancing the specific capacity during lithium insertion. Additionally, a higher concentration of oxygen vacancies boosts ionic conductivity and lithium ion diffusion kinetics, leading to superior electrochemical performance. Among the synthesized materials, Li 0.11 (CrMnCoNiZn) 2.89 O 4 exhibited the best performance, delivering a discharge capacity of 365 mAh·g −1 after 100 cycles at 100 mA·g −1 , 257 mAh·g −1 after 1000 cycles at 1 A·g −1 , and a rate capacity of 196 mAh·g −1 at 2 A·g −1 . The Li + diffusion coefficient reached 2.78 × 10 −15 cm 2 ·s −1 . This work not only deepens the understanding of HEOs' electrochemical behavior in LIBs but also provides insights into the impact of lithium ion substitution on their performance.

25 ENERGY STORAGE↗

Spinel-Structured High Entropy Oxides: Low Temperature Synthesis, Characterization, and Potential Applications

High entropy oxides (HEOs) have recently attracted increasing attention due to their remarkable properties and relatively low cost. Herein we report a simple, highly scalable, and low temperature method for synthesizing spinel (FeNiCoCuZn) 3 O 4 (HEO). We heated an aqueous solution containing divalent cations in high alkali environments to temperatures of 25 - 95 °C for 24 h under atmospheric pressure. The HEO, synthesized at 95 °C for 24 h in 1 M KOH, was paramagnetic at room temperature, with a magnetic mass susceptibility of χ = (7.5 ± 0.2) × 10 –7 m 3 ·kg –1 . It demonstrated stable electrochemical lithium storage performance, with a gravimetric capacity of ∼300 mAh·g –1 at 100 mA·g –1 . It was also active in the electrocatalytic oxygen evolution reaction with an overpotential of 460 mV in alkaline media. The band gap energies were in the range of 2.4 eV. Our advancement in the synthesis and processing of transition metal-based HEOs will undoubtedly render them a viable solution for next generation materials for energy production and storage.

diffraction↗

Probing the Local Site Disorder and Distortion in Pyrochlore High-Entropy Oxides

High-entropy oxides (HEOs) have attracted great interest in diverse fields because of their inherent opportunities to tailor and combine materials functionalities. The control of local order/disorder in the class is by extension a grand challenge toward realizing their vast potential. In this paper, we report the first examples of pyrochlore HEOs with five M-site cations, for Nd 2 M 2 O 7 , in which the local structure has been investigated by neutron diffraction and pair distribution function (PDF) analysis. The average structure of the pyrochlores is found to be orthorhombic Imma, in agreement with radius-ratio rules governing the structural archetype. The computed PDFs from density functional theory relaxed special quasirandom structure models are compared with real space PDFs in this work to evaluate M-site order/disorder. Reverse Monte Carlo combined with ab initio molecular dynamics and Metropolis Monte Carlo simulations demonstrates that Nd 2 (Ta 0.2 Sc 0.2 Sn 0.2 Hf 0.2 Zr 0.2 ) 2 O 7 is synthesized with its M-site local to nanoscale order highly randomized/disordered, while Nd 2 (Ti 0.2 Nb 0.2 Sn 0.2 Hf 0.2 Zr 0.2 ) 2 O 7+x exhibits a strong distortion of the TiO 6 octahedron and small degree of Ti chemical short-range order (SRO) on the subnanometer scale. Calculations suggest that this may be intrinsic, energetically favored SRO rather than due to sample processing. These results offer an important demonstration that the engineered variation of participating ions in HEOs, even among those with very similar radii, provides richly diverse opportunities to control local order/disorder motifs—and therefore materials properties for future designs. This work also hints at the exquisite level of detail that may be needed in computational and experimental data analysis to guide structure–property tuning in the emerging HEO materials class.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct observation of elemental fluctuation and oxygen octahedral distortion-dependent charge distribution in high entropy oxides

The enhanced compositional flexibility to incorporate multiple-principal cations in high entropy oxides (HEOs) offers the opportunity to expand boundaries for accessible compositions and unconventional properties in oxides. Attractive functionalities have been reported in some bulk HEOs, which are attributed to the long-range compositional homogeneity, lattice distortion, and local chemical bonding characteristics in materials. However, the intricate details of local composition fluctuation, metal-oxygen bond distortion and covalency are difficult to visualize experimentally, especially on the atomic scale. Here, we study the atomic structure-chemical bonding-property correlations in a series of perovskite-HEOs utilizing the recently developed four-dimensional scanning transmission electron microscopy techniques which enables to determine the structure, chemical bonding, electric field, and charge density on the atomic scale. The existence of compositional fluctuations along with significant composition-dependent distortion of metal-oxygen bonds is observed. Consequently, distinct variations of metal-oxygen bonding covalency are shown by the real-space charge-density distribution maps with sub-ångström resolution. The observed atomic features not only provide a realistic picture of the local physico-chemistry of chemically complex HEOs but can also be directly correlated to their distinctive magneto-electronic properties.

36 MATERIALS SCIENCE↗

Synergistic effects of mixing and strain in high entropy spinel oxides for oxygen evolution reaction

Developing stable and efficient electrocatalysts is vital for boosting oxygen evolution reaction (OER) rates in sustainable hydrogen production. High-entropy oxides (HEOs) consist of five or more metal cations, providing opportunities to tune their catalytic properties toward high OER efficiency. This work combines theoretical and experimental studies to scrutinize the OER activity and stability for spinel-type HEOs. Density functional theory confirms that randomly mixed metal sites show thermodynamic stability, with intermediate adsorption energies displaying wider distributions due to mixing-induced equatorial strain in active metal-oxygen bonds. The rapid sol-flame method is employed to synthesize HEO, comprising five 3d-transition metal cations, which exhibits superior OER activity and durability under alkaline conditions, outperforming lower-entropy oxides, even with partial surface oxidations. The study highlights that the enhanced activity of HEO is primarily attributed to the mixing of multiple elements, leading to strain effects near the active site, as well as surface composition and coverage.

08 HYDROGEN↗

Computational insights into hydrogen adsorption energies on medium-entropy oxides

High entropy oxides (HEOs) have emerged as promising catalysts for several important chemical transformations including alkane activation. Hydrogen adsorption energy (HAE) has been used as a key descriptor for many reactions including methane C–H activation and hydrogen evolution reactions. Hence, understanding the relationship between HAEs and the surface chemistry of HEO surfaces could lay the foundation for meaningful correlations among methane C–H activation, HAE, and the complex, local environment of HEO surfaces. Here, we used a medium-entropy oxide as a prototypical system – Mg 0.25 Ni 0.25 Cu 0.25 Zn 0.25 O with a rock-salt structure – to interrogate these relationships. We sampled 2000 different surfaces of its (100) plane and calculated the HAEs at randomly chosen surface O sites using density functional theory (DFT). Our analysis of the 2000 data points reveals that the HAEs at the surface O sites are significantly influenced by the local environment around the adsorption sites, particularly the nature of the metal atom directly below the surface O site where H adsorbs. After comparing several popular graph-neural-network-based machine learning models, we found that the DimeNet++ model performed best achieving satisfactory accuracy in predicting HAEs for both Mg 0.25 Ni 0.25 Cu 0.25 Zn 0.25 O and slightly varied compositions. Our work underscores the promise of such models and the need for further refinement to address the complexity of HEOs.

Song, Haohong [Vanderbilt Univ., Nashville, TN (Un↗

High entropy oxides prediction and discovery by the Mixed Enthalpy-Entropy Descriptor

The vast, high-dimensional composition space of high-entropy oxides (HEOs) offers exceptional opportunities for functional materials discovery, yet it also poses a fundamental challenge: the rational and efficient prediction of stable, synthesizable compositions and the corresponding structure–property relationships. Despite growing interest, the field still lacks broadly applicable, physically grounded descriptors capable of navigating various large chemical spaces. Here, we introduce a Mixed Enthalpy–Entropy Descriptor (MEED) that enables rapid, first-principles–based prediction of HEOs synthesizability across diverse chemistries. Using MEED, we perform high-throughput screening of two distinct HEO families: rocksalt oxides and perovskite oxides. The predicted top candidates in each family were experimentally validated. MEED reveals unifying thermodynamic and structural principles governing stability across both chemical compositions and polymorphs, providing mechanistic insight into the formation of high-entropy phases. This work significantly broadens the accessible chemical design space for HEOs and establishes a data-efficient framework for accelerating the discovery of next-generation functional materials.

Yu, Liping [University of Central Florida]↗