Defects, Dopants and Sodium Mobility in Na2MnSiO4

Navaratnarajah Kuganathan; Alexander Chroneos

doi:10.1038/s41598-018-32856-7

Defects, Dopants and Sodium Mobility in Na₂MnSiO₄

Navaratnarajah Kuganathan, Alexander Chroneos

College of Engineering, Environment & Science

Imperial College London

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

33 Citations (Scopus)

59 Downloads (Pure)

Abstract

Sodium manganese orthosilicate, Na₂MnSiO₄, is a promising positive electrode material in rechargeable sodium ion batteries. Atomistic scale simulations are used to study the defects, doping behaviour and sodium migration paths in Na₂MnSiO₄. The most favourable intrinsic defect type is the cation anti-site (0.44 eV/defect), in which, Na and Mn exchange their positions. The second most favourable defect energy process is found to be the Na Frenkel (1.60 eV/defect) indicating that Na diffusion is assisted by the formation of Na vacancies via the vacancy mechanism. Long range sodium paths via vacancy mechanism were constructed and it is confirmed that the lowest activation energy (0.81 eV) migration path is three dimensional with zig-zag pattern. Subvalent doping by Al on the Si site is energetically favourable suggesting that this defect engineering stratergy to increase the Na content in Na₂MnSiO₄ warrants experimental verification.

Original language	English
Article number	14669
Number of pages	7
Journal	Scientific Reports
Volume	8
Issue number	1
Early online date	2 Oct 2018
DOIs	https://doi.org/10.1038/s41598-018-32856-7
Publication status	Published - 1 Dec 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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abstract = "Sodium manganese orthosilicate, Na2MnSiO4, is a promising positive electrode material in rechargeable sodium ion batteries. Atomistic scale simulations are used to study the defects, doping behaviour and sodium migration paths in Na2MnSiO4. The most favourable intrinsic defect type is the cation anti-site (0.44 eV/defect), in which, Na and Mn exchange their positions. The second most favourable defect energy process is found to be the Na Frenkel (1.60 eV/defect) indicating that Na diffusion is assisted by the formation of Na vacancies via the vacancy mechanism. Long range sodium paths via vacancy mechanism were constructed and it is confirmed that the lowest activation energy (0.81 eV) migration path is three dimensional with zig-zag pattern. Subvalent doping by Al on the Si site is energetically favourable suggesting that this defect engineering stratergy to increase the Na content in Na2MnSiO4 warrants experimental verification.",

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