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Title: Calibrating transition-metal energy levels and oxygen bands in first-principles calculations: Accurate prediction of redox potentials and charge transfer in lithium transition-metal oxides

Abstract

Transition-metal (TM) oxides play an increasingly important role in technology today, including applications such as catalysis, solar energy harvesting, and energy storage. In many of these applications, the details of their electronic structure near the Fermi level are critically important for their properties. We propose a first-principles–based computational methodology for the accurate prediction of oxygen charge transfer in TM oxides and lithium TM (Li-TM) oxides. To obtain accurate electronic structures, the Heyd-Scuseria-Ernzerhof (HSE06) hybrid functional is adopted, and the amount of exact Hartree-Fock exchange (mixing parameter) is adjusted to reproduce reference band gaps. We show that the HSE06 functional with optimal mixing parameter yields not only improved electronic densities of states, but also better energetics (Li-intercalation voltages) for LiCoO 2 and LiNiO 2 as compared to the generalized gradient approximation (GGA), Hubbard U corrected GGA (GGA + U), and standard HSE06. We find that the optimal mixing parameters for TM oxides are system specific and correlate with the covalency (ionicity) of the TM species. The strong covalent (ionic) nature of TM-O bonding leads to lower (higher) optimal mixing parameters. We find that optimized HSE06 functionals predict stronger hybridization of the Co 3d and O 2p orbitals as compared to GGA,more » resulting in a greater contribution from oxygen states to charge compensation upon delithiation in LiCoO 2. We also find that the band gaps of Li-TM oxides increase linearly with the mixing parameter, enabling the straightforward determination of optimal mixing parameters based on GGA (α = 0.0) and HSE06 (α = 0.25) calculations. Our results also show that G 0 W 0 @ GGA + U band gaps of TM oxides ( M O , M = Mn , Co , Ni ) and LiCoO 2 agree well with experimental references, suggesting that G 0 W 0 calculations can be used as a reference for the calibration of the mixing parameter in cases when no experimental band gap has been reported.« less

Authors:
 [1];  [1];  [2]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering; Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Publication Date:
Research Org.:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE; National Research Foundation of Korea (NRF)
OSTI Identifier:
1505755
Alternate Identifier(s):
OSTI ID: 1214339
Grant/Contract Number:  
FG02-96ER45571
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review. B, Condensed Matter and Materials Physics
Additional Journal Information:
Journal Volume: 92; Journal Issue: 11; Journal ID: ISSN 1098-0121
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Seo, Dong-Hwa, Urban, Alexander, and Ceder, Gerbrand. Calibrating transition-metal energy levels and oxygen bands in first-principles calculations: Accurate prediction of redox potentials and charge transfer in lithium transition-metal oxides. United States: N. p., 2015. Web. doi:10.1103/physrevb.92.115118.
Seo, Dong-Hwa, Urban, Alexander, & Ceder, Gerbrand. Calibrating transition-metal energy levels and oxygen bands in first-principles calculations: Accurate prediction of redox potentials and charge transfer in lithium transition-metal oxides. United States. doi:10.1103/physrevb.92.115118.
Seo, Dong-Hwa, Urban, Alexander, and Ceder, Gerbrand. Tue . "Calibrating transition-metal energy levels and oxygen bands in first-principles calculations: Accurate prediction of redox potentials and charge transfer in lithium transition-metal oxides". United States. doi:10.1103/physrevb.92.115118. https://www.osti.gov/servlets/purl/1505755.
@article{osti_1505755,
title = {Calibrating transition-metal energy levels and oxygen bands in first-principles calculations: Accurate prediction of redox potentials and charge transfer in lithium transition-metal oxides},
author = {Seo, Dong-Hwa and Urban, Alexander and Ceder, Gerbrand},
abstractNote = {Transition-metal (TM) oxides play an increasingly important role in technology today, including applications such as catalysis, solar energy harvesting, and energy storage. In many of these applications, the details of their electronic structure near the Fermi level are critically important for their properties. We propose a first-principles–based computational methodology for the accurate prediction of oxygen charge transfer in TM oxides and lithium TM (Li-TM) oxides. To obtain accurate electronic structures, the Heyd-Scuseria-Ernzerhof (HSE06) hybrid functional is adopted, and the amount of exact Hartree-Fock exchange (mixing parameter) is adjusted to reproduce reference band gaps. We show that the HSE06 functional with optimal mixing parameter yields not only improved electronic densities of states, but also better energetics (Li-intercalation voltages) for LiCoO2 and LiNiO2 as compared to the generalized gradient approximation (GGA), Hubbard U corrected GGA (GGA + U), and standard HSE06. We find that the optimal mixing parameters for TM oxides are system specific and correlate with the covalency (ionicity) of the TM species. The strong covalent (ionic) nature of TM-O bonding leads to lower (higher) optimal mixing parameters. We find that optimized HSE06 functionals predict stronger hybridization of the Co 3d and O 2p orbitals as compared to GGA, resulting in a greater contribution from oxygen states to charge compensation upon delithiation in LiCoO2. We also find that the band gaps of Li-TM oxides increase linearly with the mixing parameter, enabling the straightforward determination of optimal mixing parameters based on GGA (α = 0.0) and HSE06 (α = 0.25) calculations. Our results also show that G0 W0 @ GGA + U band gaps of TM oxides ( M O , M = Mn , Co , Ni ) and LiCoO2 agree well with experimental references, suggesting that G0 W0 calculations can be used as a reference for the calibration of the mixing parameter in cases when no experimental band gap has been reported.},
doi = {10.1103/physrevb.92.115118},
journal = {Physical Review. B, Condensed Matter and Materials Physics},
number = 11,
volume = 92,
place = {United States},
year = {2015},
month = {9}
}

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Works referenced in this record:

Reversible anionic redox chemistry in high-capacity layered-oxide electrodes
journal, July 2013

  • Sathiya, M.; Rousse, G.; Ramesha, K.
  • Nature Materials, Vol. 12, Issue 9
  • DOI: 10.1038/nmat3699

Electronic structure of CoO, Li-doped CoO, and LiCoO 2
journal, September 1991


Can short-range hybrids describe long-range-dependent properties?
journal, July 2009

  • Henderson, Thomas M.; Izmaylov, Artur F.; Scalmani, Giovanni
  • The Journal of Chemical Physics, Vol. 131, Issue 4
  • DOI: 10.1063/1.3185673

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Electrochemical extraction of lithium from LiMn2O4
journal, February 1984


Efficient hybrid density functional calculations in solids: Assessment of the Heyd–Scuseria–Ernzerhof screened Coulomb hybrid functional
journal, July 2004

  • Heyd, Jochen; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 121, Issue 3, p. 1187-1192
  • DOI: 10.1063/1.1760074

First-principles modeling of localized d states with the G W @ LDA + U approach
journal, July 2010


Degree of covalency of LiCoO2: X-ray emission and photoelectron study
journal, July 1996


Hybrid functionals based on a screened Coulomb potential
journal, May 2003

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 118, Issue 18
  • DOI: 10.1063/1.1564060

Band gaps and electronic structure of transition-metal compounds
journal, July 1985


Energy band gaps and lattice parameters evaluated with the Heyd-Scuseria-Ernzerhof screened hybrid functional
journal, November 2005

  • Heyd, Jochen; Peralta, Juan E.; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 123, Issue 17
  • DOI: 10.1063/1.2085170

Range Separation and Local Hybridization in Density Functional Theory
journal, December 2008

  • Henderson, Thomas M.; Janesko, Benjamin G.; Scuseria, Gustavo E.
  • The Journal of Physical Chemistry A, Vol. 112, Issue 49
  • DOI: 10.1021/jp806573k

Local hybrid functionals based on density matrix products
journal, October 2007

  • Janesko, Benjamin G.; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 127, Issue 16
  • DOI: 10.1063/1.2784406

Erratum: “Screened hybrid density functionals applied to solids” [J. Chem. Phys. 124, 154709 (2006)]
journal, December 2006

  • Paier, J.; Marsman, M.; Hummer, K.
  • The Journal of Chemical Physics, Vol. 125, Issue 24
  • DOI: 10.1063/1.2403866

Charge transport in lithium peroxide: relevance for rechargeable metal–air batteries
journal, January 2013

  • Radin, Maxwell D.; Siegel, Donald J.
  • Energy & Environmental Science, Vol. 6, Issue 8
  • DOI: 10.1039/c3ee41632a

Testing variations of the GW approximation on strongly correlated transition metal oxides: hematite (α-Fe2O3) as a benchmark
journal, January 2011

  • Liao, Peilin; Carter, Emily A.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 33
  • DOI: 10.1039/c1cp20829b

Iron-Based Layered Superconductor La[O 1- x F x ]FeAs ( x = 0.05−0.12) with T c = 26 K
journal, March 2008

  • Kamihara, Yoichi; Watanabe, Takumi; Hirano, Masahiro
  • Journal of the American Chemical Society, Vol. 130, Issue 11
  • DOI: 10.1021/ja800073m

First-principles prediction of redox potentials in transition-metal compounds with LDA + U
journal, December 2004


The origin of ferroelectricity in magnetoelectric YMnO3
journal, February 2004

  • Van Aken, Bas B.; Palstra, Thomas T. M.; Filippetti, Alessio
  • Nature Materials, Vol. 3, Issue 3
  • DOI: 10.1038/nmat1080

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

  • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
  • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
  • DOI: 10.1103/PhysRevB.57.1505

Electronic Structure of Chemically-Delithiated LiCoO 2 Studied by Electron Energy-Loss Spectrometry
journal, February 2002

  • Graetz, J.; Hightower, A.; Ahn, C. C.
  • The Journal of Physical Chemistry B, Vol. 106, Issue 6
  • DOI: 10.1021/jp0133283

Electron correlation in semiconductors and insulators: Band gaps and quasiparticle energies
journal, October 1986


Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators
journal, August 1995


Hybrid functional study on structural and electronic properties of oxides
journal, May 2011


Effect of exchange and correlation on bulk properties of MgO, NiO, and CoO
journal, February 2000


Electronic structure of Li-doped NiO
journal, January 1992


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
  • DOI: 10.1088/0953-8984/9/4/002

Self-consistent generalized Kohn-Sham local hybrid functionals of screened exchange: Combining local and range-separated hybridization
journal, September 2008

  • Janesko, Benjamin G.; Krukau, Aliaksandr V.; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 129, Issue 12
  • DOI: 10.1063/1.2980056

CoO2, The End Member of the LixCoO2 Solid Solution
journal, January 1996

  • Amatucci, G. G.; Tarascon, J. M.; Klein, L. C.
  • Journal of The Electrochemical Society, Vol. 143, Issue 3, p. 1114-1123
  • DOI: 10.1149/1.1836594

Origin of voltage decay in high-capacity layered oxide electrodes
journal, December 2014

  • Sathiya, M.; Abakumov, A. M.; Foix, D.
  • Nature Materials, Vol. 14, Issue 2
  • DOI: 10.1038/nmat4137

The insulator-metal transition upon lithium deintercalation from LiCoO2: electronic properties and 7Li NMR study
journal, January 1999

  • Ménétrier, Michel; Saadoune, Ismael; Levasseur, Stéphane
  • Journal of Materials Chemistry, Vol. 9, Issue 5
  • DOI: 10.1039/a900016j

Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)]
journal, June 2006

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 124, Issue 21
  • DOI: 10.1063/1.2204597

First-principles investigation of phase stability in Li x CoO 2
journal, August 1998


Hole localization in Al doped silica: A DFT+U description
journal, October 2006

  • Nolan, Michael; Watson, Graeme W.
  • The Journal of Chemical Physics, Vol. 125, Issue 14
  • DOI: 10.1063/1.2354468

Cobalt(III) lithium oxide, CoLiO2: structure refinement by powder neutron diffraction
journal, January 1984

  • Orman, H. J.; Wiseman, P. J.
  • Acta Crystallographica Section C Crystal Structure Communications, Vol. 40, Issue 1, p. 12-14
  • DOI: 10.1107/S0108270184002833

The electronic structure of alkali doped alkaline earth metal oxides: Li doping of MgO studied with DFT-GGA and GGA+U
journal, July 2005


Correlation of lithium ion distribution and X-ray absorption near-edge structure in O3- and O2-lithium cobalt oxides from first-principle calculation
journal, January 2012

  • Okumura, Toyoki; Yamaguchi, Yoichi; Shikano, Masahiro
  • Journal of Materials Chemistry, Vol. 22, Issue 33
  • DOI: 10.1039/c2jm32024j

A New Sealed Lithium-Peroxide Battery with a Co-Doped Li2O Cathode in a Superconcentrated Lithium Bis(fluorosulfonyl)amide Electrolyte
journal, July 2014

  • Okuoka, Shin-ichi; Ogasawara, Yoshiyuki; Suga, Yosuke
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep05684

A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles
journal, October 2011


High-capacity electrode materials for rechargeable lithium batteries: Li 3 NbO 4 -based system with cation-disordered rocksalt structure
journal, June 2015

  • Yabuuchi, Naoaki; Takeuchi, Mitsue; Nakayama, Masanobu
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 25
  • DOI: 10.1073/pnas.1504901112

Hybrid schemes combining the Hartree–Fock method and density-functional theory: Underlying formalism and properties of correlation functionals
journal, February 1997

  • Görling, Andreas; Levy, Mel
  • The Journal of Chemical Physics, Vol. 106, Issue 7
  • DOI: 10.1063/1.473369

Electronic structure of defective lithium cobaltites Li x CoO2
journal, October 2008


Hybrid density functional calculations of redox potentials and formation energies of transition metal compounds
journal, August 2010


Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries
journal, April 1997

  • Padhi, A. K.
  • Journal of The Electrochemical Society, Vol. 144, Issue 4, p. 1188-1194
  • DOI: 10.1149/1.1837571

Ab initio calculation of the intercalation voltage of lithium-transition-metal oxide electrodes for rechargeable batteries
journal, October 1997


Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965


Linear response approach to the calculation of the effective interaction parameters in the LDA + U method
journal, January 2005


Designing New Lithium-Excess Cathode Materials from Percolation Theory: Nanohighways in Li x Ni 2–4 x /3 Sb x /3 O 2
journal, December 2014

  • Twu, Nancy; Li, Xin; Urban, Alexander
  • Nano Letters, Vol. 15, Issue 1
  • DOI: 10.1021/nl5040754

Significant Reduction in NiO Band Gap Upon Formation of Li x Ni 1− x O alloys: Applications To Solar Energy Conversion
journal, November 2013

  • Alidoust, Nima; Toroker, Maytal Caspary; Keith, John A.
  • ChemSusChem, Vol. 7, Issue 1
  • DOI: 10.1002/cssc.201300595

Phase diagrams of lithium transition metal oxides: investigations from first principles
journal, September 1999


Electronic structure of 3d-transition-metal oxides: on-site Coulomb repulsion versus covalency
journal, January 1999

  • Zimmermann, R.; Steiner, P.; Claessen, R.
  • Journal of Physics: Condensed Matter, Vol. 11, Issue 7
  • DOI: 10.1088/0953-8984/11/7/002

A first-order Mott transition in LixCoO2
journal, August 2004

  • Marianetti, C. A.; Kotliar, G.; Ceder, G.
  • Nature Materials, Vol. 3, Issue 9
  • DOI: 10.1038/nmat1178

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Accurate screened exchange band structures for the transition metal monoxides MnO, FeO, CoO and NiO
journal, April 2013


Electronic structure of 3 d -transition-metal compounds by analysis of the 2 p core-level photoemission spectra
journal, August 1992


Different oxygen redox participation for bulk and surface: A possible global explanation for the cycling mechanism of Li1.20Mn0.54Co0.13Ni0.13O2
journal, August 2013


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Density-functional modelling of core-hole effects in electron energy-loss near-edge spectra
journal, February 2001


Electronic structure of MnO
journal, July 1991


Influence of the exchange screening parameter on the performance of screened hybrid functionals
journal, December 2006

  • Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F.
  • The Journal of Chemical Physics, Vol. 125, Issue 22
  • DOI: 10.1063/1.2404663

Metal-insulator transitions
journal, October 1998

  • Imada, Masatoshi; Fujimori, Atsushi; Tokura, Yoshinori
  • Reviews of Modern Physics, Vol. 70, Issue 4, p. 1039-1263
  • DOI: 10.1103/RevModPhys.70.1039

Low hole polaron migration barrier in lithium peroxide
journal, February 2012


Charge disproportionation and Jahn-Teller distortion in LiNiO 2 and NaNiO 2 : A density functional theory study
journal, August 2011


Local hybrid functionals
journal, January 2003

  • Jaramillo, Juanita; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 118, Issue 3
  • DOI: 10.1063/1.1528936

Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999

  • Adamo, Carlo; Barone, Vincenzo
  • The Journal of Chemical Physics, Vol. 110, Issue 13
  • DOI: 10.1063/1.478522

Electron-energy-loss core-edge structures in manganese oxides
journal, July 1993


Ab initio study of lithium intercalation in metal oxides and metal dichalcogenides
journal, July 1997


Identification of cathode materials for lithium batteries guided by first-principles calculations
journal, April 1998

  • Ceder, G.; Chiang, Y. -M.; Sadoway, D. R.
  • Nature, Vol. 392, Issue 6677
  • DOI: 10.1038/33647

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
  • DOI: 10.1103/PhysRevB.44.943

Density functional theory study of MnO by a hybrid functional approach
journal, July 2005


Oxygen Contribution on Li-Ion Intercalation−Deintercalation in LiCoO 2 Investigated by O K-Edge and Co L-Edge X-ray Absorption Spectroscopy
journal, March 2002

  • Yoon, Won-Sub; Kim, Kwang-Bum; Kim, Min-Gyu
  • The Journal of Physical Chemistry B, Vol. 106, Issue 10
  • DOI: 10.1021/jp013735e

Formation enthalpies by mixing GGA and GGA + U calculations
journal, July 2011


Excitonic Effects in Core-Excitation Spectra of Semiconductors
journal, September 2000


Comparative Study on the Performance of Hybrid DFT Functionals in Highly Correlated Oxides: The Case of CeO 2 and Ce 2 O 3
journal, December 2010

  • Graciani, Jesús; Márquez, Antonio M.; Plata, José J.
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 1
  • DOI: 10.1021/ct100430q

Magnitude and Origin of the Band Gap in NiO
journal, December 1984


Multiferroics: a magnetic twist for ferroelectricity
journal, January 2007

  • Cheong, Sang-Wook; Mostovoy, Maxim
  • Nature Materials, Vol. 6, Issue 1
  • DOI: 10.1038/nmat1804

Lithium batteries: a new tool in solid state chemistry
journal, April 1999


Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal–air batteries
journal, June 2011

  • Suntivich, Jin; Gasteiger, Hubert A.; Yabuuchi, Naoaki
  • Nature Chemistry, Vol. 3, Issue 7, p. 546-550
  • DOI: 10.1038/nchem.1069

Variation of optical gaps in perovskite-type 3 d transition-metal oxides
journal, December 1993


Rationale for mixing exact exchange with density functional approximations
journal, December 1996

  • Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron
  • The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985
  • DOI: 10.1063/1.472933

Quasiparticle band structures of the antiferromagnetic transition-metal oxides MnO, FeO, CoO, and NiO
journal, June 2009


Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001

In situ X-ray absorption spectroscopic study of Li-rich layered cathode material Li[Ni0.17Li0.2Co0.07Mn0.56]O2
journal, August 2011


Oxygen and transition metal involvement in the charge compensation mechanism of LiNi1/3Mn1/3Co1/3O2 cathodes
journal, January 2012

  • Petersburg, Cole F.; Li, Zheng; Chernova, Natasha A.
  • Journal of Materials Chemistry, Vol. 22, Issue 37
  • DOI: 10.1039/c2jm33392a

Electron-energy-loss spectra of NiO
journal, May 2004


High Performance Li 2 Ru 1– y Mn y O 3 (0.2 ≤ y ≤ 0.8) Cathode Materials for Rechargeable Lithium-Ion Batteries: Their Understanding
journal, March 2013

  • Sathiya, M.; Ramesha, K.; Rousse, G.
  • Chemistry of Materials, Vol. 25, Issue 7
  • DOI: 10.1021/cm400193m