Ab initio investigations of the electronic structures and chemical bonding in LiCo{sub 6}P{sub 4} and Li{sub 2}Co{sub 12}P{sub 7}

The electronic structures of the metal-rich phosphides LiCo{sub 6}P{sub 4} and Li{sub 2}Co{sub 12}P{sub 7} were studied by DFT calculations. Both phosphides consist of three-dimensional [Co{sub 6}P{sub 4}] and [Co{sub 12}P{sub 7}] polyanionic networks which leave hexagonal channels for the lithium a...

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Bibliographic Details
Published in:Journal of solid state chemistry 2013-06, Vol.202
Main Authors: Matar, Samir F., Université de Bordeaux, ICMCB, UPR 9048, F‐33600 Pessac, Al-Alam, Adel, Ouaini, Naïm, Pöttgen, Rainer
Format: Article
Language:English
Subjects:
ATOMS
CHEMICAL BONDS
COBALT
ELECTRONIC STRUCTURE
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
LITHIUM
PHOSPHIDES
PHOSPHORUS
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Summary:The electronic structures of the metal-rich phosphides LiCo{sub 6}P{sub 4} and Li{sub 2}Co{sub 12}P{sub 7} were studied by DFT calculations. Both phosphides consist of three-dimensional [Co{sub 6}P{sub 4}] and [Co{sub 12}P{sub 7}] polyanionic networks which leave hexagonal channels for the lithium atoms. COOP data show strong Co–P and Co–Co bonding within the polyanions. The lithium atoms have trigonal prismatic phosphorus coordination. Total energy calculations indicate stability upon de-lithiation towards the Co{sub 6}P{sub 4} and Co{sub 12}P{sub 7} substructures - Graphical abstract: The cobalt–phosphorus networks in LiCo{sub 6}P{sub 4} and Li{sub 2}Co{sub 12}P{sub 7}. - Highlights: • Chemical bonding resolved in the metal-rich phosphides LiCo{sub 6}P{sub 4} and Li{sub 2}Co{sub 12}P{sub 7}. • Strong covalent Co–P bonding character in the [Co{sub 6}P{sub 4}] and [Co{sub 12}P{sub 7}] substructures. • Total energy calculations indicate stability of the de-lithiated substructures.
ISSN:0022-4596
1095-726X
DOI:10.1016/J.JSSC.2013.03.032