High‐Throughput Screening of High‐Entropy Fluorite‐Type Oxides as Potential Candidates for Photovoltaic Applications

Kumbhakar, Mukesh; Khandelwal, Anurag; Jha, Shikhar Krishn; Kante, Monaha Veerraju; Keßler, Pirmin; Lemmer, Uli; Hahn, Horst; Aghassi‐Hagmann, Jasmin; Colsmann, Alexander; Estrada, Leonardo Velasco; Velasco, Leonardo; Schweidler, Simon

doi:10.1002/aenm.202204337

Cited by 9 publications

(2 citation statements)

References 49 publications

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“…Traditional methods, where a few (5–10) compositions are made at a time, are an inefficient way to search through complex composition spaces. This need to explore complex compositions is exacerbated by the growing interest to use high entropy materials to further develop battery materials and in other energy applications. − A recent series in Nature Materials highlights many developments in high-entropy materials and points to the need for further exploration . Thoroughly studying compositions where some high-entropy combinations may be of benefit implies a requirement for a very large number of samples.…”

Section: Motivation For Increased Experimental Throughputmentioning

confidence: 99%

Semiautomated Experiments to Accelerate the Design of Advanced Battery Materials: Combining Speed, Low Cost, and Adaptability

McCalla

2023

ACS Eng. Au

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A number of methodologies are currently being exploited in order to dramatically increase the composition space explored in the design of new battery materials. This is proving necessary as commercial Li-ion battery materials have become increasingly high-performing and complex. For example, commercial cathode materials have quinary compositions with a sixth element in the coating, while a very large number of contenders are still being considered for solid electrolytes, with most of the periodic table being at play. Furthermore, the promise of accelerated design by computation and machine learning (ML) are encouraging, but they both ultimately require large amounts of quality experimental data either to fill in holes left by the computations or to be used to improve the ML models. All of this leads researchers to increase experimental throughputs. This perspective focuses on semiautomated experimental approaches where automation is only utilized in key steps where absolutely necessary in order to overcome bottlenecks while minimizing costs. Such workflows are more widely accessible to research groups as compared to fully automated systems, such that the current perspective may be useful to a wide community. The most essential steps in automation are related to characterization, with X-ray diffraction being a key bottleneck. By analyzing published workflows of both semi-and fully automated workflows, it is found herein that steps handled by researchers during the synthesis are not prohibitive in terms of overall throughput and may lead to greater flexibility, making more synthesis routes possible. Examples will be provided in this perspective of workflows that have been optimized for anodes, cathodes, and electrolytes in Li batteries, the vast majority of which are also suitable for battery technologies beyond Li.

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Section: Motivation For Increased Experimental Throughputmentioning

confidence: 99%

Semiautomated Experiments to Accelerate the Design of Advanced Battery Materials: Combining Speed, Low Cost, and Adaptability

McCalla

2023

ACS Eng. Au

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“…As a result, at temperatures exceeding 1000 • C, (Ce, La, Pr, Sm, Y)O 2−δ undergoes an ordering of these oxygen vacancies and structurally transforms from fluorite to bixbyite [29][30][31]. In a recent high-throughput study by Kumbhakar et al, Zr 4+ has been observed to stabilize the fluorite structure in rare earth high-entropy oxides [32]. However, there have been no detailed studies of the effect of Zr doping on the structure and electrochemical properties of Zr-doped (Ce, La, Pr, Sm, Y)O 2−δ .…”

Section: Introductionmentioning

confidence: 99%

Influence of Zr-doping on the structure and transport properties of rare earth high-entropy oxides

Kante,

Lakshmi Nilayam,

Kreka

et al. 2024

J. Phys. Energy

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Fluorite-type ceria-based ceramics are well established as oxygen ion conductors due to their high conductivity superseding state-of-the-art electrolytes like yttria-stabilized zirconia. However, at specific temperature and oxygen partial pressure, they occasionally exhibit electronic conduction attributed to polaron hopping via multivalent cations (e.g. Pr and Ce). (Ce, La, Sm, Pr, Y)O2-δ is a high-entropy oxide with a fluorite-type structure, featuring low concentrations of multivalent cations which could potentially mitigate polaron hopping. However, (Ce, La, Sm, Pr, Y)O2-δ undergoes a structural transition to the bixbyite-type structure above 1000 °C. In this study, we introduce Zr doping into (Ce, La, Pr, Sm, Y)O2-δ to hinder the structural transition at elevated temperatures. Indeed, fluorite structure at elevated temperatures is stabilized at approximately 10 at.% Zr doping. The total conductivity initially increases with doping, peaking at 5 at.% Zr doping, and subsequently decreases with further doping. Interestingly, electronic conductivity in (Ce, La, Pr, Sm, Y)1-xZrxO2-δ under oxidizing atmospheres is not significant and is lowest at 8 at.% Zr. These results suggest that ceria-based high entropy oxides can serve as oxygen ion conductors with significantly reduced electronic contribution. This work paves the way for new compositionally complex electrolytes as well as protective coatings for solid oxide fuel cells.

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Room‐Temperature Synthesis of a Compositionally Complex Rare‐Earth Carbonate Hydroxide and its Conversion into a Bixbyite‐Type High‐Entropy Sesquioxide

Bernauer,

Trapp,

Wiehl

et al. 2023

Eur J Inorg Chem

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In the present work, the solvent‐deficient synthesis of the high‐entropy rare‐earth carbonate hydroxide RE(CO3)(OH) (RE=La, Ce, Pr, Nd, Sm, and Gd) and its thermal conversion into bixbyite‐type sesquioxide RE2O3 are reported for the first time. The high‐entropy rare earth carbonate hydroxide was prepared via mechanochemical reaction of the corresponding metal nitrate hydrates with ammonium hydrogen carbonate followed by the removal of the NH4NO3 by‐product. Calcination of the carbonate hydroxide precursor in ambient atmosphere at temperatures in the range from 500 to 1000 °C led to the high‐entropy rare earth sesquioxide which exhibited a bixbyite‐type structure ( ) independent of the calcination temperature. Transmission electron microscopy (TEM) investigation revealed the homogeneous distribution of all six rare earth cations in the high‐entropy sesquioxide lattice, however, with some compositional variation between individual grains. The bixbyite‐type structure may be considered as the result of heavy doping of the fluorite‐type CeO2 lattice with the other rare earth cations, which leads to a high concentration of oxygen vacancies, as revealed by electron diffraction and Raman spectroscopy data. The solvent‐deficient synthesis method used in the present study is considered as a valuable, straightforward and easily up‐scalable method to synthesize compositionally complex oxide ceramics.

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High‐Throughput Screening of High‐Entropy Fluorite‐Type Oxides as Potential Candidates for Photovoltaic Applications

Cited by 9 publications

References 49 publications

Semiautomated Experiments to Accelerate the Design of Advanced Battery Materials: Combining Speed, Low Cost, and Adaptability

Semiautomated Experiments to Accelerate the Design of Advanced Battery Materials: Combining Speed, Low Cost, and Adaptability

Influence of Zr-doping on the structure and transport properties of rare earth high-entropy oxides

Room‐Temperature Synthesis of a Compositionally Complex Rare‐Earth Carbonate Hydroxide and its Conversion into a Bixbyite‐Type High‐Entropy Sesquioxide

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