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

Abstract

First-principles density functional calculations were used to calculate surface properties of the LiMn 2O 4 spinel. The calculations were benchmarked to obtain the correct semiconducting, Jahn-Teller distorted electronic ground state of bulk LiMn 2O 4 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 LiMn 2O 4 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.

Authors:
 [1];  [1];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1511355
Alternate Identifier(s):
OSTI ID: 1102361
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Review. B, Condensed Matter and Materials Physics
Additional Journal Information:
Journal Volume: 87; Journal Issue: 7; Journal ID: ISSN 1098-0121
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Karim, Altaf, Fosse, Sonia, and Persson, Kristin A. Surface structure and equilibrium particle shape of the LiMn2O4 spinel from first-principles calculations. United States: N. p., 2013. Web. doi:10.1103/PhysRevB.87.075322.
Karim, Altaf, Fosse, Sonia, & Persson, Kristin A. Surface structure and equilibrium particle shape of the LiMn2O4 spinel from first-principles calculations. United States. doi:10.1103/PhysRevB.87.075322.
Karim, Altaf, Fosse, Sonia, and Persson, Kristin A. Fri . "Surface structure and equilibrium particle shape of the LiMn2O4 spinel from first-principles calculations". United States. doi:10.1103/PhysRevB.87.075322. https://www.osti.gov/servlets/purl/1511355.
@article{osti_1511355,
title = {Surface structure and equilibrium particle shape of the LiMn2O4 spinel from first-principles calculations},
author = {Karim, Altaf and Fosse, Sonia and Persson, Kristin A.},
abstractNote = {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.},
doi = {10.1103/PhysRevB.87.075322},
journal = {Physical Review. B, Condensed Matter and Materials Physics},
issn = {1098-0121},
number = 7,
volume = 87,
place = {United States},
year = {2013},
month = {2}
}

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Cited by: 55 works
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Works referenced in this record:

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