Surface structure and equilibrium particle shape of the LiMn O spinel from first-principles calculations
Abstract
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.
- Authors:
-
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE
- OSTI Identifier:
- 1511355
- Alternate Identifier(s):
- OSTI ID: 1102361
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- 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. https://doi.org/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. https://doi.org/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},
number = 7,
volume = 87,
place = {United States},
year = {Fri Feb 15 00:00:00 EST 2013},
month = {Fri Feb 15 00:00:00 EST 2013}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 111 works
Citation information provided by
Web of Science
Web of Science
Figures / Tables:
FIG. 1: The unit cell of the LiMn2O4 cubic spinel structure indicating the positions of the Li (blue), the Mn (magenta) and O (red) atomic species.
All figures and tables
(7 total)
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Improved Elevated Temperature Cycling of LiMn[sub 2]O[sub 4] Spinel Through the Use of a Composite LiF-Based Electrolyte
journal, January 2001
- Sun, X.; Lee, H. S.; Yang, X. Q.
- Electrochemical and Solid-State Letters, Vol. 4, Issue 11
Prediction of solid-aqueous equilibria: Scheme to combine first-principles calculations of solids with experimental aqueous states
journal, June 2012
- Persson, Kristin A.; Waldwick, Bryn; Lazic, Predrag
- Physical Review B, Vol. 85, Issue 23
Tailoring the Morphology of LiCoO 2 : A First Principles Study
journal, August 2009
- Kramer, Denis; Ceder, Gerbrand
- Chemistry of Materials, Vol. 21, Issue 16
Improved capacity retention in rechargeable 4 V lithium/lithium-manganese oxide (spinel) cells
journal, April 1994
- Gummow, R. J.; de Kock, A.; Thackeray, M. M.
- Solid State Ionics, Vol. 69, Issue 1, p. 59-67
Mott transition of MnO under pressure: A comparison of correlated band theories
journal, November 2006
- Kasinathan, Deepa; Kuneš, J.; Koepernik, K.
- Physical Review B, Vol. 74, Issue 19
Jahn–Teller distortion and electronic structure of LiMn2O4
journal, April 2009
- Ouyang, C. Y.; Shi, S. Q.; Lei, M. S.
- Journal of Alloys and Compounds, Vol. 474, Issue 1-2
Preparation of fine single crystals of spinel-type lithium manganese oxide by LiCl flux method for rechargeable lithium batteries. Part 1. LiMn2O4
journal, August 2002
- Tang, Weiping; Yang, Xiaojing; Liu, Zhonghui
- Journal of Materials Chemistry, Vol. 12, Issue 10
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Electronic Crystallization in a Lithium Battery Material: Columnar Ordering of Electrons and Holes in the Spinel
journal, November 1998
- Rodríguez-Carvajal, J.; Rousse, G.; Masquelier, C.
- Physical Review Letters, Vol. 81, Issue 21
Manganese oxides for lithium batteries
journal, January 1997
- Thackeray, Michael M.
- Progress in Solid State Chemistry, Vol. 25, Issue 1-2
Structural Fatigue in Spinel Electrodes in High Voltage (4 V) Li/Li[sub x]Mn[sub 2]O[sub 4] Cells
journal, January 1999
- Thackeray, Michael M.
- Electrochemical and Solid-State Letters, Vol. 1, Issue 1
Atomistic simulation of mineral surfaces: Studies of surface stability and growth
journal, May 1997
- Parker, S. C.; Oliver, P. M.; De Leeuw, N. H.
- Phase Transitions, Vol. 61, Issue 1-4
Special points for Brillouin-zone integrations
journal, June 1976
- Monkhorst, Hendrik J.; Pack, James D.
- Physical Review B, Vol. 13, Issue 12, p. 5188-5192
First-principles study of surface properties of : Surface energy, structure, Wulff shape, and surface redox potential
journal, October 2007
- Wang, L.; Zhou, F.; Meng, Y. S.
- Physical Review B, Vol. 76, Issue 16
Oxidation States of Mn Atoms at Clean and Al 2 O 3 -Covered LiMn 2 O 4 (001) Surfaces
journal, March 2010
- Ouyang, C. Y.; Zeng, X. M.; Šljivancanin, Ž.
- The Journal of Physical Chemistry C, Vol. 114, Issue 10
Simulation of the surface structure of lithium manganese oxide spinel
journal, May 2011
- Benedek, R.; Thackeray, M. M.
- Physical Review B, Vol. 83, Issue 19
Phase transformations and volume changes in spinel LixMn2O4
journal, November 2000
- Van der Ven, A.
- Solid State Ionics, Vol. 135, Issue 1-4
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Polarity of oxide surfaces and nanostructures
journal, December 2007
- Goniakowski, Jacek; Finocchi, Fabio; Noguera, Claudine
- Reports on Progress in Physics, Vol. 71, Issue 1
Li Metal-Free Rechargeable Batteries Based on Li[sub 1+x]Mn[sub 2]O[sub 4] Cathodes (0 ≤ x ≤ 1) and Carbon Anodes
journal, January 1991
- Tarascon, J. M.
- Journal of The Electrochemical Society, Vol. 138, Issue 10
The electronic structure and band gap of LiFePO4 and LiMnPO4
journal, October 2004
- Zhou, Fei; Kang, Kisuk; Maxisch, Thomas
- Solid State Communications, Vol. 132, Issue 3-4
Spinel Electrodes from the Li-Mn-O System for Rechargeable Lithium Battery Applications
journal, January 1992
- Thackeray, M. M.
- Journal of The Electrochemical Society, Vol. 139, Issue 2
Lithium insertion into manganese spinels
journal, April 1983
- Thackeray, M. M.; David, W. I. F.; Bruce, P. G.
- Materials Research Bulletin, Vol. 18, Issue 4, p. 461-472
Band theory and Mott insulators: Hubbard U instead of Stoner I
journal, July 1991
- Anisimov, Vladimir I.; Zaanen, Jan; Andersen, Ole K.
- Physical Review B, Vol. 44, Issue 3, p. 943-954
Spinel Electrodes for Lithium Batteries
journal, December 1999
- Thackeray, Michael M.
- Journal of the American Ceramic Society, Vol. 82, Issue 12
LiMn2O4 cathode doped with excess lithium and synthesized by co-precipitation for Li-ion batteries
journal, March 2003
- Chan, H. W.; Duh, J. G.; Sheen, S. R.
- Journal of Power Sources, Vol. 115, Issue 1
Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation
journal, September 1992
- Perdew, John P.; Chevary, J. A.; Vosko, S. H.
- Physical Review B, Vol. 46, Issue 11
First-principles calculations of the electronic structure and spectra of strongly correlated systems: the LDA + U method
journal, January 1997
- Anisimov, Vladimir I.; Aryasetiawan, F.; Lichtenstein, A. I.
- Journal of Physics: Condensed Matter, Vol. 9, Issue 4, p. 767-808
Correlating Capacity Fading and Structural Changes in Li[sub 1+y]Mn[sub 2−y]O[sub 4−δ] Spinel Cathode Materials: A Systematic Study on the Effects of Li/Mn Ratio and Oxygen Deficiency
journal, January 2001
- Xia, Yongyao; Sakai, Tetsuo; Fujieda, Takuya
- Journal of The Electrochemical Society, Vol. 148, Issue 7
Highly crystalline lithium–manganese spinel prepared by a hydrothermal process with co-solvent
journal, February 2011
- Lee, Jae-Won; Kim, Jun-Il; Min, Sung Hwan
- Journal of Power Sources, Vol. 196, Issue 3
Charge and spin ordering in
journal, August 2001
- Tomeno, Izumi; Kasuya, Yusuke; Tsunoda, Yorihiko
- Physical Review B, Vol. 64, Issue 9
Self-Discharge of LiMn[sub 2]O[sub 4]/C Li-Ion Cells in Their Discharged State
journal, January 1998
- Blyr, A.
- Journal of The Electrochemical Society, Vol. 145, Issue 1
Factors affecting Li mobility in spinel LiMn2O4—A first-principles study by GGA and GGA+U methods
journal, August 2010
- Xu, Bo; Meng, Shirley
- Journal of Power Sources, Vol. 195, Issue 15
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Density-functional theory and NiO photoemission spectra
journal, December 1993
- Anisimov, V. I.; Solovyev, I. V.; Korotin, M. A.
- Physical Review B, Vol. 48, Issue 23
An Investigation of Spinel-Related and Orthorhombic LiMnO[sub 2] Cathodes for Rechargeable Lithium Batteries
journal, January 1994
- Gummow, R. J.
- Journal of The Electrochemical Society, Vol. 141, Issue 5
The stability of ionic crystal surfaces
journal, November 1979
- Tasker, P. W.
- Journal of Physics C: Solid State Physics, Vol. 12, Issue 22
Structural and electronic properties of under pressure: An ab initio study
journal, January 2005
- Trimarchi, G.; Binggeli, N.
- Physical Review B, Vol. 71, Issue 3
Correlating Capacity Loss of Stoichiometric and Nonstoichiometric Lithium Manganese Oxide Spinel Electrodes with Their Structural Integrity
journal, January 1999
- Huang, Haitao
- Journal of The Electrochemical Society, Vol. 146, Issue 10
Dynamic Structural Changes at LiMn 2 O 4 /Electrolyte Interface during Lithium Battery Reaction
journal, November 2010
- Hirayama, Masaaki; Ido, Hedekazu; Kim, KyungSu
- Journal of the American Chemical Society, Vol. 132, Issue 43
Orbital Ordering in : Electron-Electron versus Electron-Lattice Interactions
journal, March 2006
- Yin, Wei-Guo; Volja, Dmitri; Ku, Wei
- Physical Review Letters, Vol. 96, Issue 11
Structure and electrochemical characterization of Li1+xMn2−xO4 spinels for rechargeable lithium batteries
journal, September 1999
- Takada, Toshimi; Hayakawa, Hiroshi; Enoki, Hirotoshi
- Journal of Power Sources, Vol. 81-82
Ab initio calculation of the intercalation voltage of lithium-transition-metal oxide electrodes for rechargeable batteries
journal, October 1997
- Aydinol, M. K.; Kohan, A. F.; Ceder, G.
- Journal of Power Sources, Vol. 68, Issue 2
Works referencing / citing this record:
Surface Structural Transition Induced by Gradient Polyanion-Doping in Li-Rich Layered Oxides: Implications for Enhanced Electrochemical Performance
journal, May 2016
- Zhao, Ying; Liu, Jiatu; Wang, Shuangbao
- Advanced Functional Materials, Vol. 26, Issue 26
Impact of High Valence State Cation Ti/Ta Surface Doping on the Stabilization of Spinel LiNi 0.5 Mn 1.5 O 4 Cathode Materials: A Systematic Density Functional Theory Investigation
journal, April 2018
- Chen, Yuyang; Ben, Liubin; Chen, Bin
- Advanced Materials Interfaces, Vol. 5, Issue 12
Nonequilibrium Pathways during Electrochemical Phase Transformations in Single Crystals Revealed by Dynamic Chemical Imaging at Nanoscale Resolution
journal, December 2014
- Yu, Young-Sang; Kim, Chunjoong; Liu, Yijin
- Advanced Energy Materials, Vol. 5, Issue 7
Suppressing Manganese Dissolution from Lithium Manganese Oxide Spinel Cathodes with Single-Layer Graphene
journal, June 2015
- Jaber-Ansari, Laila; Puntambekar, Kanan P.; Kim, Soo
- Advanced Energy Materials, Vol. 5, Issue 17
Computer Simulation of Cathode Materials for Lithium Ion and Lithium Batteries: A Review
journal, September 2018
- Ma, Ying
- Energy & Environmental Materials, Vol. 1, Issue 3
Unravelling structural ambiguities in lithium- and manganese-rich transition metal oxides
journal, October 2015
- Shukla, Alpesh Khushalchand; Ramasse, Quentin M.; Ophus, Colin
- Nature Communications, Vol. 6, Issue 1
Size-dependent kinetics during non-equilibrium lithiation of nano-sized zinc ferrite
journal, January 2019
- Li, Jing; Meng, Qingping; Zhang, Yiman
- Nature Communications, Vol. 10, Issue 1
A perspective on the high-voltage LiMn1.5Ni0.5O4 spinel cathode for lithium-ion batteries
journal, January 2014
- Manthiram, Arumugam; Chemelewski, Katharine; Lee, Eun-Sung
- Energy & Environmental Science, Vol. 7, Issue 4
First-principles study on thermodynamic stability of the hybrid interfacial structure of LiMn 2 O 4 cathode and carbonate electrolyte in Li-ion batteries
journal, January 2018
- Choi, Daehyeon; Kang, Joonhee; Park, Jinwoo
- Physical Chemistry Chemical Physics, Vol. 20, Issue 17
Effect of composition on the structure of lithium- and manganese-rich transition metal oxides
journal, January 2018
- Shukla, Alpesh Khushalchand; Ramasse, Quentin M.; Ophus, Colin
- Energy & Environmental Science, Vol. 11, Issue 4
Influence of particle size on the apparent electrocatalytic activity of LiMn 2 O 4 for oxygen evolution
journal, January 2019
- Baumung, Max; Schönewald, Florian; Erichsen, Torben
- Sustainable Energy & Fuels, Vol. 3, Issue 9
Understanding the loss of electrochemical activity of nanosized LiMn 2 O 4 particles: a combined experimental and ab initio DFT study
journal, January 2018
- Velásquez, Ever A.; Silva, Daiane P. B.; Falqueto, Juliana B.
- Journal of Materials Chemistry A, Vol. 6, Issue 30
Ethylene carbonate adsorption on the major surfaces of lithium manganese oxide Li 1−x Mn 2 O 4 spinel (0.000 < x < 0.375): a DFT+ U -D3 study
journal, January 2020
- Ramogayana, Brian; Santos-Carballal, David; Aparicio, Pablo A.
- Physical Chemistry Chemical Physics, Vol. 22, Issue 12
Effects of surface stability on the morphological transformation of metals and metal oxides as investigated by first-principles calculations
journal, September 2015
- Andrés, Juan; Gracia, Lourdes; Gouveia, Amanda Fernandes
- Nanotechnology, Vol. 26, Issue 40
Theoretical Insights into Oxidation States of Transition Metals at (001) and (111) LiNi 0.5 Mn 1.5 O 4 Spinel Surfaces
journal, January 2018
- Intan, Nadia N.; Klyukin, Konstantin; Alexandrov, Vitaly
- Journal of The Electrochemical Society, Vol. 165, Issue 5
Figures / Tables found in this record:
Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.