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Title: Structure and electron density analysis of electrochemically and chemically delithiated LiCoO{sub 2} single crystals

Abstract

Single crystals of Li{sub 0.68}CoO{sub 2}, Li{sub 0.48}CoO{sub 2}, and Li{sub 0.35}CoO{sub 2} were successfully synthesized for the first time by means of electrochemical and chemical delithiation processes using LiCoO{sub 2} single crystals as a parent compound. A single-crystal X-ray diffraction study confirmed the trigonal R3-barm space group and the hexagonal lattice parameters a=2.8107(5) A, c=14.2235(6) A, and c/a=5.060 for Li{sub 0.68}CoO{sub 2}; a=2.8090(15) A, c=14.3890(17) A, and c/a=5.122 for Li{sub 0.48}CoO{sub 2}; and a=2.8070(12) A, c=14.4359(14) A, and c/a=5.143 for Li{sub 0.35}CoO{sub 2}. The crystal structures were refined to the conventional values R=1.99% and wR=1.88% for Li{sub 0.68}CoO{sub 2}; R=2.40% and wR=2.58% for Li{sub 0.48}CoO{sub 2}; and R=2.63% and wR=2.56% for Li{sub 0.35}CoO{sub 2}. The oxygen-oxygen contact distance in the CoO{sub 6} octahedron was determined to be shortened by the delithiation from 2.6180(9) A in LiCoO{sub 2} to 2.5385(15) A in Li{sub 0.35}CoO{sub 2}. The electron density distributions of these Li {sub x} CoO{sub 2} crystals were analyzed by the maximum entropy method (MEM) using the present single-crystal X-ray diffraction data at 300 K. From the results of the single-crystal MEM, strong covalent bonding was clearly visible between the Co and O atoms, while no bonding was found aroundmore » the Li atoms in these compounds. The gradual decrease in the electron density at the Li site upon delithiation could be precisely analyzed. - Graphical abstract: Three-dimensional electron density distribution of the electrochemically delithiated Li{sub 0.68}CoO{sub 2} obtained by the maximum entropy method (MEM) using single-crystal X-ray diffraction data.« less

Authors:
 [1];  [1];  [2];  [2];  [2];  [3]
  1. National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba 305-8565 (Japan)
  2. Graduate School of Engineering, Tohoku University, Aramaki-Aoba, Aoba-ku, Sendai 980-8579 (Japan)
  3. National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba 305-8565 (Japan), E-mail: j.akimoto@aist.go.jp
Publication Date:
OSTI Identifier:
21015653
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 1; Other Information: DOI: 10.1016/j.jssc.2006.10.018; PII: S0022-4596(06)00552-4; Copyright (c) 2006 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CALCULATION METHODS; COBALT OXIDES; COVALENCE; ELECTROCHEMISTRY; ELECTROMECHANICS; ELECTRON DENSITY; ENTROPY; HEXAGONAL LATTICES; LITHIUM OXIDES; MICROSTRUCTURE; MONOCRYSTALS; SPACE GROUPS; TRIGONAL LATTICES; X-RAY DIFFRACTION

Citation Formats

Takahashi, Yasuhiko, Kijima, Norihito, Dokko, Kaoru, Nishizawa, Matsuhiko, Uchida, Isamu, and Akimoto, Junji. Structure and electron density analysis of electrochemically and chemically delithiated LiCoO{sub 2} single crystals. United States: N. p., 2007. Web. doi:10.1016/j.jssc.2006.10.018.
Takahashi, Yasuhiko, Kijima, Norihito, Dokko, Kaoru, Nishizawa, Matsuhiko, Uchida, Isamu, & Akimoto, Junji. Structure and electron density analysis of electrochemically and chemically delithiated LiCoO{sub 2} single crystals. United States. doi:10.1016/j.jssc.2006.10.018.
Takahashi, Yasuhiko, Kijima, Norihito, Dokko, Kaoru, Nishizawa, Matsuhiko, Uchida, Isamu, and Akimoto, Junji. Mon . "Structure and electron density analysis of electrochemically and chemically delithiated LiCoO{sub 2} single crystals". United States. doi:10.1016/j.jssc.2006.10.018.
@article{osti_21015653,
title = {Structure and electron density analysis of electrochemically and chemically delithiated LiCoO{sub 2} single crystals},
author = {Takahashi, Yasuhiko and Kijima, Norihito and Dokko, Kaoru and Nishizawa, Matsuhiko and Uchida, Isamu and Akimoto, Junji},
abstractNote = {Single crystals of Li{sub 0.68}CoO{sub 2}, Li{sub 0.48}CoO{sub 2}, and Li{sub 0.35}CoO{sub 2} were successfully synthesized for the first time by means of electrochemical and chemical delithiation processes using LiCoO{sub 2} single crystals as a parent compound. A single-crystal X-ray diffraction study confirmed the trigonal R3-barm space group and the hexagonal lattice parameters a=2.8107(5) A, c=14.2235(6) A, and c/a=5.060 for Li{sub 0.68}CoO{sub 2}; a=2.8090(15) A, c=14.3890(17) A, and c/a=5.122 for Li{sub 0.48}CoO{sub 2}; and a=2.8070(12) A, c=14.4359(14) A, and c/a=5.143 for Li{sub 0.35}CoO{sub 2}. The crystal structures were refined to the conventional values R=1.99% and wR=1.88% for Li{sub 0.68}CoO{sub 2}; R=2.40% and wR=2.58% for Li{sub 0.48}CoO{sub 2}; and R=2.63% and wR=2.56% for Li{sub 0.35}CoO{sub 2}. The oxygen-oxygen contact distance in the CoO{sub 6} octahedron was determined to be shortened by the delithiation from 2.6180(9) A in LiCoO{sub 2} to 2.5385(15) A in Li{sub 0.35}CoO{sub 2}. The electron density distributions of these Li {sub x} CoO{sub 2} crystals were analyzed by the maximum entropy method (MEM) using the present single-crystal X-ray diffraction data at 300 K. From the results of the single-crystal MEM, strong covalent bonding was clearly visible between the Co and O atoms, while no bonding was found around the Li atoms in these compounds. The gradual decrease in the electron density at the Li site upon delithiation could be precisely analyzed. - Graphical abstract: Three-dimensional electron density distribution of the electrochemically delithiated Li{sub 0.68}CoO{sub 2} obtained by the maximum entropy method (MEM) using single-crystal X-ray diffraction data.},
doi = {10.1016/j.jssc.2006.10.018},
journal = {Journal of Solid State Chemistry},
number = 1,
volume = 180,
place = {United States},
year = {Mon Jan 15 00:00:00 EST 2007},
month = {Mon Jan 15 00:00:00 EST 2007}
}