Local electronic structure of layered LixNi0.5Mn 0.5O2 and LixNi1/3Mn 1/3Co1/3O2

Shu Miao, Michael Kocher, Peter Rez, Brent Fultz, Yasunori Ozawa, Rachid Yazami, Channing C. Ahn

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

Samples of LixNi0.5Mn0.5O2 and LixNi1/3Mn1/3Co1/3O2 were prepared as active materials in electrochemical half-cells and were cycled electrochemically to obtain different values of Li concentration, x. Absorption edges of Ni, Mn, Co, and O in these materials of differing x were measured by electron energy loss spectrometry (EELS) in a transmission electron microscope to determine the changes in local electronic structure caused by delithiation. The work was supported by electronic structure calculations with the VASP pseudopotential package, the full-potential linear augmented plane wave code WIEN2K, and atomic multiplet calculations that took account of the electronic effects from local octahedral symmetry. A valence change from Ni2+ to Ni4+ with delithiation would have caused a 3 eV shift in energy of the intense white line at the Ni L3 edge, but the measured shift was less than 1.2 eV, The intensities of the "white lines" at the Ni L-edges did not change enough to account for a substantial change of Ni valence. No changes were detectable at the Mn and Co L-edges after delithiation either. Both EELS and the computational efforts showed that most of the charge compensation for Li+ takes place at hybridized O 2p states, not at Ni atoms.

Original languageEnglish (US)
Pages (from-to)23473-23479
Number of pages7
JournalJournal of Physical Chemistry B
Volume109
Issue number49
DOIs
StatePublished - Dec 15 2005

Fingerprint

Spectrometry
Electronic structure
Energy dissipation
electronic structure
Electrons
Electron microscopes
energy dissipation
electron energy
valence
Atoms
shift
spectroscopy
pseudopotentials
plane waves
electron microscopes
fine structure
symmetry
cells
electronics
atoms

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Local electronic structure of layered LixNi0.5Mn 0.5O2 and LixNi1/3Mn 1/3Co1/3O2 . / Miao, Shu; Kocher, Michael; Rez, Peter; Fultz, Brent; Ozawa, Yasunori; Yazami, Rachid; Ahn, Channing C.

In: Journal of Physical Chemistry B, Vol. 109, No. 49, 15.12.2005, p. 23473-23479.

Research output: Contribution to journalArticle

Miao, S, Kocher, M, Rez, P, Fultz, B, Ozawa, Y, Yazami, R & Ahn, CC 2005, 'Local electronic structure of layered LixNi0.5Mn 0.5O2 and LixNi1/3Mn 1/3Co1/3O2 ', Journal of Physical Chemistry B, vol. 109, no. 49, pp. 23473-23479. https://doi.org/10.1021/jp0542266
Miao, Shu ; Kocher, Michael ; Rez, Peter ; Fultz, Brent ; Ozawa, Yasunori ; Yazami, Rachid ; Ahn, Channing C. / Local electronic structure of layered LixNi0.5Mn 0.5O2 and LixNi1/3Mn 1/3Co1/3O2 In: Journal of Physical Chemistry B. 2005 ; Vol. 109, No. 49. pp. 23473-23479.
@article{7bc569b9d6fa40fcad7ea2d13aaa307d,
title = "Local electronic structure of layered LixNi0.5Mn 0.5O2 and LixNi1/3Mn 1/3Co1/3O2",
abstract = "Samples of LixNi0.5Mn0.5O2 and LixNi1/3Mn1/3Co1/3O2 were prepared as active materials in electrochemical half-cells and were cycled electrochemically to obtain different values of Li concentration, x. Absorption edges of Ni, Mn, Co, and O in these materials of differing x were measured by electron energy loss spectrometry (EELS) in a transmission electron microscope to determine the changes in local electronic structure caused by delithiation. The work was supported by electronic structure calculations with the VASP pseudopotential package, the full-potential linear augmented plane wave code WIEN2K, and atomic multiplet calculations that took account of the electronic effects from local octahedral symmetry. A valence change from Ni2+ to Ni4+ with delithiation would have caused a 3 eV shift in energy of the intense white line at the Ni L3 edge, but the measured shift was less than 1.2 eV, The intensities of the {"}white lines{"} at the Ni L-edges did not change enough to account for a substantial change of Ni valence. No changes were detectable at the Mn and Co L-edges after delithiation either. Both EELS and the computational efforts showed that most of the charge compensation for Li+ takes place at hybridized O 2p states, not at Ni atoms.",
author = "Shu Miao and Michael Kocher and Peter Rez and Brent Fultz and Yasunori Ozawa and Rachid Yazami and Ahn, {Channing C.}",
year = "2005",
month = "12",
day = "15",
doi = "10.1021/jp0542266",
language = "English (US)",
volume = "109",
pages = "23473--23479",
journal = "Journal of Physical Chemistry B Materials",
issn = "1520-6106",
publisher = "American Chemical Society",
number = "49",

}

TY - JOUR

T1 - Local electronic structure of layered LixNi0.5Mn 0.5O2 and LixNi1/3Mn 1/3Co1/3O2

AU - Miao, Shu

AU - Kocher, Michael

AU - Rez, Peter

AU - Fultz, Brent

AU - Ozawa, Yasunori

AU - Yazami, Rachid

AU - Ahn, Channing C.

PY - 2005/12/15

Y1 - 2005/12/15

N2 - Samples of LixNi0.5Mn0.5O2 and LixNi1/3Mn1/3Co1/3O2 were prepared as active materials in electrochemical half-cells and were cycled electrochemically to obtain different values of Li concentration, x. Absorption edges of Ni, Mn, Co, and O in these materials of differing x were measured by electron energy loss spectrometry (EELS) in a transmission electron microscope to determine the changes in local electronic structure caused by delithiation. The work was supported by electronic structure calculations with the VASP pseudopotential package, the full-potential linear augmented plane wave code WIEN2K, and atomic multiplet calculations that took account of the electronic effects from local octahedral symmetry. A valence change from Ni2+ to Ni4+ with delithiation would have caused a 3 eV shift in energy of the intense white line at the Ni L3 edge, but the measured shift was less than 1.2 eV, The intensities of the "white lines" at the Ni L-edges did not change enough to account for a substantial change of Ni valence. No changes were detectable at the Mn and Co L-edges after delithiation either. Both EELS and the computational efforts showed that most of the charge compensation for Li+ takes place at hybridized O 2p states, not at Ni atoms.

AB - Samples of LixNi0.5Mn0.5O2 and LixNi1/3Mn1/3Co1/3O2 were prepared as active materials in electrochemical half-cells and were cycled electrochemically to obtain different values of Li concentration, x. Absorption edges of Ni, Mn, Co, and O in these materials of differing x were measured by electron energy loss spectrometry (EELS) in a transmission electron microscope to determine the changes in local electronic structure caused by delithiation. The work was supported by electronic structure calculations with the VASP pseudopotential package, the full-potential linear augmented plane wave code WIEN2K, and atomic multiplet calculations that took account of the electronic effects from local octahedral symmetry. A valence change from Ni2+ to Ni4+ with delithiation would have caused a 3 eV shift in energy of the intense white line at the Ni L3 edge, but the measured shift was less than 1.2 eV, The intensities of the "white lines" at the Ni L-edges did not change enough to account for a substantial change of Ni valence. No changes were detectable at the Mn and Co L-edges after delithiation either. Both EELS and the computational efforts showed that most of the charge compensation for Li+ takes place at hybridized O 2p states, not at Ni atoms.

UR - http://www.scopus.com/inward/record.url?scp=30644456573&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=30644456573&partnerID=8YFLogxK

U2 - 10.1021/jp0542266

DO - 10.1021/jp0542266

M3 - Article

VL - 109

SP - 23473

EP - 23479

JO - Journal of Physical Chemistry B Materials

JF - Journal of Physical Chemistry B Materials

SN - 1520-6106

IS - 49

ER -