Surface structure and equilibrium particle shape of the LiMn2O4 spinel from first-principles calculations

Karim, Altaf; Fosse, Sonia; Persson, Kristin A.

doi:10.1103/PhysRevB.87.075322

Title: Surface structure and equilibrium particle shape of the LiMn $_{2}$ O $_{4}$ spinel from first-principles calculations

Journal Article · Fri Feb 15 00:00:00 EST 2013 · Physical Review. B, Condensed Matter and Materials Physics

DOI:https://doi.org/10.1103/PhysRevB.87.075322· OSTI ID:1511355

Karim, Altaf ^[1]; Fosse, Sonia ^[1]; Persson, Kristin A. ^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

First-principles density functional calculations were used to calculate surface properties of the LiMn₂O₄ spinel. The calculations were benchmarked to obtain the correct semiconducting, Jahn-Teller distorted electronic ground state of bulk LiMn₂O₄ and, using the same parameters, the predominant low-index polar surface facets (100), (110), and (111) were calculated to study their structure and stability. Following an investigation of possible surface terminations as well as surface layer reconstructions we find that the (111) LMO surface stabilizes through a targeted site exchange of the undercoordinated surface Mn cations with fully coordinated tetrahedral subsurface Li cations, effectively creating a partial inverse spinel arrangement at the surface. This reconstruction renders the (111) facet the most stable among the investigated facets. Here, the equilibrium (Wulff) shape of a LiMn₂O₄ particle was constructed and exhibits a cubo-octahedral shape with predominant (1 1 1) facets, in agreement with common experimental findings for the spinel structure.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1511355

Alternate ID(s):: OSTI ID: 1102361

Journal Information:: Physical Review. B, Condensed Matter and Materials Physics, Vol. 87, Issue 7; ISSN 1098-0121

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 111 works

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