Defects, Lithium Mobility and Tetravalent Dopants in the Li3NbO4 Cathode Material

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Abstract

The defect processes of oxides such as self-diffusion impact their performance in electrochemical devices such as batteries and solid oxide fuel cells. The performance of lithium ion batteries can be improved by increasing the Li-ion diffusion. In that respect Li3NbO4 is identified as a positive electrode material for rechargeable lithium ion batteries. Here, we employ static atomistic scale simulations to examine the defect properties, doping behaviour and lithium ion migration paths in Li3NbO4. The present calculations show a correct reproduction of experimentally observed crystal structure of Li3NbO4. The Li-Nb anti-site defect is found to be the dominant intrinsic defect process suggesting that a small concentration of Li on Nb sites and Nb on Li sites is present. Vacancy assisted long range lithium diffusion paths were examined and our calculations reveal that the lowest activation energy (1.13 eV) migration path is two dimensional forming a zig-zag shape. Subvalent doping by Ge on the Nb site is thermodynamically favourable process and a potential strategy to incorporate extra Li in the form of Li interstitial in Li3NbO4. The results presented herein can motivate further experimental work for the development of Li3NbO4 based batteries.
Original languageEnglish
Article number2192
Number of pages8
JournalScientific Reports
Volume9
Issue number1
DOIs
Publication statusPublished - 18 Feb 2019

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electric batteries
lithium
cathodes
defects
ions
solid oxide fuel cells
electrode materials
interstitials
activation energy
crystal structure
oxides
simulation

Bibliographical note

CC-BY Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. Te images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.
© The Author(s) 2019

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Defects, Lithium Mobility and Tetravalent Dopants in the Li3NbO4 Cathode Material. / Kuganathan, Navaratnarajah; Kordatos, Apostolos; Kelaidis, Nikolaos; Chroneos, Alexander.

In: Scientific Reports, Vol. 9, No. 1, 2192, 18.02.2019.

Research output: Contribution to journalArticle

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