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Local Electronic Structure of Layered Li_xNi_(0.5)Mn_(0.5)O_2 and Li_xNi_(1/3)Mn_(1/3)Co_(1/3)O_2

Miao, Shu and Kocher, Michael and Rez, Peter and Fultz, Brent and Ozawa, Yasunori and Yazami, Rachid and Ahn, Channing C. (2005) Local Electronic Structure of Layered Li_xNi_(0.5)Mn_(0.5)O_2 and Li_xNi_(1/3)Mn_(1/3)Co_(1/3)O_2. Journal of Physical Chemistry B, 109 (49). pp. 23473-23479. ISSN 1520-6106. doi:10.1021/jp0542266.

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Samples of Li_xNi_(0.5)Mn_(0.5)O_2 and Li_xNi_(1/3)Mn_(1/3)Co_(1/3)O_2 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 Ni^(2+) to Ni^(4+) with delithiation would have caused a 3 eV shift in energy of the intense white line at the Ni L_3 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.

Item Type:Article
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Fultz, Brent0000-0002-6364-8782
Yazami, Rachid0000-0002-0085-5012
Additional Information:© 2005 American Chemical Society. Received 29 July 2005. Published online 17 November 2005. Published in print 1 December 2005. We thank Dr. F. M. F. de Groot for use of the multiplet codes and B. J. A. Nourish for computer assistance. We are grateful to Tanaka Chemicals Inc. (Japan) for providing Ni_(0.5)Mn_(0.5)(OH)_2 and Enax Inc. (Japan) for providing LiNi_(1/3)Mn_(1/3)Co_(1/3)O_2 used in this study. This work was supported by the U.S. Department of Energy under Grants DE-FG03-00ER15035 and DEFG0203ER15425.
Funding AgencyGrant Number
Department of Energy (DOE)DE-FG03-00ER15035
Department of Energy (DOE)DE-FG02-03ER15425
Issue or Number:49
Record Number:CaltechAUTHORS:20170711-104503643
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Official Citation:Local Electronic Structure of Layered LixNi0.5Mn0.5O2 and LixNi1/3Mn1/3Co1/3O2 Shu Miao, Michael Kocher, Peter Rez, Brent Fultz, Yasunori Ozawa, Rachid Yazami, and Channing C. Ahn The Journal of Physical Chemistry B 2005 109 (49), 23473-23479 DOI: 10.1021/jp0542266
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:78941
Deposited By: Ruth Sustaita
Deposited On:11 Jul 2017 21:51
Last Modified:15 Nov 2021 17:44

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