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Title: Theoretical Study of the Structural Evolution of a Na 2 FeMn(CN) 6 Cathode upon Na Intercalation

Journal Article · · Chemistry of Materials
 [1];  [1];  [1];  [1];  [1]
  1. Department of Chemistry and the Institute for Computational and Engineering Sciences and ‡Texas Material Institute and Materials Science and Engineering Program, University of Texas at Austin, Austin, Texas 78712, United States
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The Prussian Blue analog, NaxFeMn(CN)6, is a potential new cathode material for Na-ion batteries. During Na intercalation, the dehydrated material exhibits a monoclinic to rhombohedral phase transition, while the hydrated material remains in the monoclinic phase. With density functional theory calculations, the phase transition is explained in terms of a competition between Coulomb attraction, Pauli repulsion, and d–π covalent bonding. The interstitial Na cations have a strong Coulomb attraction to the N anions in the host material, which tend to bend the Mn–N bonds and reduce the volume of the structure. The presence of lattice H2O enhances the Pauli repulsion so that the volume reduction is suppressed. The calculated volume change, as it depends upon the presence of lattice H2O, is consistent with experimental measurements. Furthermore, a new LiFeMn(CN)6 phase is predicted where MnN6 octahedra decompose into LiN4 and MnN4 edge-sharing tetrahedra.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Understanding Charge Separation and Transfer at Interfaces in Energy Materials (CST)
Sponsoring Organization:
USDOE Advanced Research Projects Agency - Energy (ARPA-E); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0001091
OSTI ID:
1179738
Alternate ID(s):
OSTI ID: 1370058
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Vol. 27 Journal Issue: 10; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 82 works
Citation information provided by
Web of Science

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