Defects, Dopants and Lithium Mobility in Li 9 v 3 (P 2 O 7 ) 3 (PO 4 ) 2

Navaratnarajah Kuganathan; Sashikesh Ganeshalingam; Alexander Chroneos

doi:10.1038/s41598-018-26597-w

Defects, Dopants and Lithium Mobility in Li ₉ v ₃ (P ₂ O ₇ ) ₃ (PO ₄ ) ₂

Navaratnarajah Kuganathan, Sashikesh Ganeshalingam, Alexander Chroneos

Faculty of Engineering, Environment & Computing

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

22 Citations (Scopus)

24 Downloads (Pure)

Abstract

Layered Li₉V₃(P₂O₇)₃(PO₄)₂ has attracted considerable interest as a novel cathode material for potential use in rechargeable lithium batteries. The defect chemistry, doping behavior and lithium diffusion paths in Li₉V₃(P₂O₇)₃(PO₄)₂ are investigated using atomistic scale simulations. Here we show that the activation energy for Li migration via the vacancy mechanism is 0.72 eV along the c-Axis. Additionally, the most favourable intrinsic defect type is Li Frenkel (0.44 eV/defect) ensuring the formation of Li vacancies that are required for Li diffusion via the vacancy mechanism. The only other intrinsic defect mechanism that is close in energy is the formation of anti-site defect, in which Li and V ions exchange their positions (1.02 eV/defect) and this can play a role at higher temperatures. Considering the solution of tetravalent dopants it is calculated that they require considerable solution energies, however, the solution of GeO₂ will reduce the activation energy of migration to 0.66 eV.

Original language	English
Article number	8140
Journal	Scientific Reports
Volume	8
Issue number	1
DOIs	https://doi.org/10.1038/s41598-018-26597-w
Publication status	Published - 25 May 2018

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. 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 = "Layered Li9V3(P2O7)3(PO4)2 has attracted considerable interest as a novel cathode material for potential use in rechargeable lithium batteries. The defect chemistry, doping behavior and lithium diffusion paths in Li9V3(P2O7)3(PO4)2 are investigated using atomistic scale simulations. Here we show that the activation energy for Li migration via the vacancy mechanism is 0.72 eV along the c-Axis. Additionally, the most favourable intrinsic defect type is Li Frenkel (0.44 eV/defect) ensuring the formation of Li vacancies that are required for Li diffusion via the vacancy mechanism. The only other intrinsic defect mechanism that is close in energy is the formation of anti-site defect, in which Li and V ions exchange their positions (1.02 eV/defect) and this can play a role at higher temperatures. Considering the solution of tetravalent dopants it is calculated that they require considerable solution energies, however, the solution of GeO2 will reduce the activation energy of migration to 0.66 eV.",

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