Lithium diffusion in Li5FeO4

Navaratnarajah Kuganathan; Poobalasuntharam Iyngaran; Alexander Chroneos

doi:10.1038/s41598-018-24168-7

Lithium diffusion in Li₅FeO₄

Navaratnarajah Kuganathan, Poobalasuntharam Iyngaran, Alexander Chroneos

Faculty of Engineering, Environment & Computing

Research output: Contribution to journal › Article › peer-review

32 Citations (Scopus)

33 Downloads (Pure)

Abstract

The anti-fluorite type Li₅FeO₄ has attracted significant interest as a potential cathode material for Li ion batteries due to its high Li content and electrochemical performance. Atomic scale simulation techniques have been employed to study the defects and Li ion migration in Li₅FeO₄. The calculations suggest that the most favorable intrinsic defect type is calculated to be the cation anti-site defect, in which Li⁺ and Fe³⁺ ions exchange positions. Li Frenkel is also found to be lower in this material (0.85 eV/defect). Long range lithium diffusion paths were constructed in Li₅FeO₄ and it is confirmed that the lower migration paths are three dimensional with the lowest activation energy of migration at 0.45 eV. Here we show that doping by Si on the Fe site is energetically favourable and an efficient way to introduce a high concentration of lithium vacancies. The introduction of Si increases the migration energy barrier of Li in the vicinity of the dopant to 0.59 eV. Nevertheless, the introduction of Si is positive for the diffusivity as the migration energy barrier increase is lower less than that of the lithium Frenkel process, therefore the activation energy of Li diffusion.

Original language	English
Article number	5832
Number of pages	7
Journal	Scientific Reports
Volume	8
Issue number	1
DOIs	https://doi.org/10.1038/s41598-018-24168-7
Publication status	Published - 11 Apr 2018

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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. The 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/.

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Cite this

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title = "Lithium diffusion in Li5FeO4",

abstract = "The anti-fluorite type Li5FeO4 has attracted significant interest as a potential cathode material for Li ion batteries due to its high Li content and electrochemical performance. Atomic scale simulation techniques have been employed to study the defects and Li ion migration in Li5FeO4. The calculations suggest that the most favorable intrinsic defect type is calculated to be the cation anti-site defect, in which Li+ and Fe3+ ions exchange positions. Li Frenkel is also found to be lower in this material (0.85 eV/defect). Long range lithium diffusion paths were constructed in Li5FeO4 and it is confirmed that the lower migration paths are three dimensional with the lowest activation energy of migration at 0.45 eV. Here we show that doping by Si on the Fe site is energetically favourable and an efficient way to introduce a high concentration of lithium vacancies. The introduction of Si increases the migration energy barrier of Li in the vicinity of the dopant to 0.59 eV. Nevertheless, the introduction of Si is positive for the diffusivity as the migration energy barrier increase is lower less than that of the lithium Frenkel process, therefore the activation energy of Li diffusion.",

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