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Title: Unified View of the Local Cation-Ordered State in Inverse Spinel Oxides

Abstract

Cation ordering/disordering in spinel oxides plays a necessary role in the rich physical and chemical properties which are hallmarks of the structural archetype. A variety of cation-ordering motifs have been reported for spinel oxides with multiple cations residing on the octahedral site (or B-site). This has attracted tremendous attention from both experimental and theoretical communities in the last few decades. Yet, no unified view has been reached, presumably due to the richness of cation species and corresponding complex arrangements emergent in this large family of compounds. Here, local cation-ordered ground states of (inverse) spinel oxides with two different cations on the octahedral site have been thoroughly investigated using neutron and X-ray total scattering, and a comprehensive theory has been proposed to explain the commonly observed cation-ordered polymorphs. It is found that a cation-zigzag-ordered structure (space group P4122) is the ground state for inverse spinel oxides with a pure or strong ionic lattice, while a cation-linear-ordered arrangement (space group Imma) emerges when one of the B-site cations forms very strong directional covalent bonds with lattice oxygen. The degree and length scale of cation ordering is strongly correlated with the charge and ionic radius difference between the two octahedral site cations. Moremore » complicated cation ordering schemes can be formed when there is a concomitant charge and orbital ordering which fall on a similar energy scale. This can lead to the formation of orbital-driven cation clusters or the broad concept of “molecules” in solid- state compounds. It is anticipated these findings will help to better understand the observed physical properties of spinel oxides and thus facilitate design strategies for improved functional materials.« less

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [4];  [5];  [5]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States); Chinese Academy of Sciences (CAS), Beijing (China)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States)
  5. Chinese Academy of Sciences (CAS), Beijing (China)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
OSTI Identifier:
1571426
Report Number(s):
BNL-212229-2019-JAAM
Journal ID: ISSN 0020-1669
Grant/Contract Number:  
SC0012704; AC05-00OR22725; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Name: Inorganic Chemistry; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Liu, Jue, Wang, Xuelong, Borkiewicz, Olaf J., Hu, Enyuan, Xiao, Rui-Juan, Chen, Liquan, and Page, Katharine. Unified View of the Local Cation-Ordered State in Inverse Spinel Oxides. United States: N. p., 2019. Web. doi:10.1021/acs.inorgchem.9b01685.
Liu, Jue, Wang, Xuelong, Borkiewicz, Olaf J., Hu, Enyuan, Xiao, Rui-Juan, Chen, Liquan, & Page, Katharine. Unified View of the Local Cation-Ordered State in Inverse Spinel Oxides. United States. doi:10.1021/acs.inorgchem.9b01685.
Liu, Jue, Wang, Xuelong, Borkiewicz, Olaf J., Hu, Enyuan, Xiao, Rui-Juan, Chen, Liquan, and Page, Katharine. Fri . "Unified View of the Local Cation-Ordered State in Inverse Spinel Oxides". United States. doi:10.1021/acs.inorgchem.9b01685.
@article{osti_1571426,
title = {Unified View of the Local Cation-Ordered State in Inverse Spinel Oxides},
author = {Liu, Jue and Wang, Xuelong and Borkiewicz, Olaf J. and Hu, Enyuan and Xiao, Rui-Juan and Chen, Liquan and Page, Katharine},
abstractNote = {Cation ordering/disordering in spinel oxides plays a necessary role in the rich physical and chemical properties which are hallmarks of the structural archetype. A variety of cation-ordering motifs have been reported for spinel oxides with multiple cations residing on the octahedral site (or B-site). This has attracted tremendous attention from both experimental and theoretical communities in the last few decades. Yet, no unified view has been reached, presumably due to the richness of cation species and corresponding complex arrangements emergent in this large family of compounds. Here, local cation-ordered ground states of (inverse) spinel oxides with two different cations on the octahedral site have been thoroughly investigated using neutron and X-ray total scattering, and a comprehensive theory has been proposed to explain the commonly observed cation-ordered polymorphs. It is found that a cation-zigzag-ordered structure (space group P4122) is the ground state for inverse spinel oxides with a pure or strong ionic lattice, while a cation-linear-ordered arrangement (space group Imma) emerges when one of the B-site cations forms very strong directional covalent bonds with lattice oxygen. The degree and length scale of cation ordering is strongly correlated with the charge and ionic radius difference between the two octahedral site cations. More complicated cation ordering schemes can be formed when there is a concomitant charge and orbital ordering which fall on a similar energy scale. This can lead to the formation of orbital-driven cation clusters or the broad concept of “molecules” in solid- state compounds. It is anticipated these findings will help to better understand the observed physical properties of spinel oxides and thus facilitate design strategies for improved functional materials.},
doi = {10.1021/acs.inorgchem.9b01685},
journal = {Inorganic Chemistry},
number = ,
volume = ,
place = {United States},
year = {2019},
month = {10}
}

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This content will become publicly available on October 18, 2020
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