Mapping Structural Changes in Electrode Materials: Application of the Hybrid Eigenvector-Following Density Functional Theory (DFT) Method to Layered Li0.5MnO2

Ieuan D. Seymour; Sudip Chakraborty; Derek S. Middlemiss; David J. Wales; Clare P. Grey

doi:10.1021/acs.chemmater.5b01674

Mapping Structural Changes in Electrode Materials: Application of the Hybrid Eigenvector-Following Density Functional Theory (DFT) Method to Layered Li_0.5MnO₂

Ieuan D. Seymour, Sudip Chakraborty, Derek S. Middlemiss, David J. Wales, Clare P. Grey^*

^*Corresponding author for this work

Chemistry

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

22 Citations (Scopus)

Abstract

The migration mechanism associated with the initial layered-to-spinel transformation of partially delithiated layered LiMnO₂ was studied using hybrid eigenvector-following coupled with density functional theory. The initial part of the transformation mechanism of Li_0.5MnO₂ involves the migration of Li into both octahedral and tetrahedral local minima within the layered structure. The next stage of the transformation process involves the migration of Mn and was found to occur through several local minima, including an intermediate square pyramidal MnO₅ configuration and an independent Mn³⁺ to Mn²⁺ charge-transfer process. The migration pathways were found to be significantly affected by the size of the supercell used and the inclusion of a Hubbard U parameter in the DFT functional. The transition state searching methodology described should be useful for studying the structural rearrangements that can occur in electrode materials during battery cycling, and more generally, ionic and electronic transport phenomena in a wide range of energy materials.

Original language	English
Pages (from-to)	5550-5561
Number of pages	12
Journal	Chemistry of Materials
Volume	27
Issue number	16
DOIs	https://doi.org/10.1021/acs.chemmater.5b01674
Publication status	Published - 3 Aug 2015

Bibliographical note

Publisher Copyright:
© 2015 American Chemical Society.

Acknowledgement: Via our membership of the U.K.'s HPC Materials Chemistry Consortium, which is funded by EPSRC (No. EP/L000202), this work made use of the facilities of HECToR and ARCHER, the U.K.'s national high-performance computing service, which is funded by the Office of Science and Technology through EPSRC's High End Computing Programme. Research was also carried out at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886. C.P.G acknowledges the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award #DE-SC0012583. I.D.S. would like to acknowledge funding from the Geoffrey Moorhouse Gibson Studentship in Chemistry from Trinity College Cambridge. S.C. would like to acknowledge Carl Tryggers Stiftelse for Vetenskaplig Forskning (CTS) and Rajeev Ahuja.

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title = "Mapping Structural Changes in Electrode Materials: Application of the Hybrid Eigenvector-Following Density Functional Theory (DFT) Method to Layered Li0.5MnO2",

abstract = "The migration mechanism associated with the initial layered-to-spinel transformation of partially delithiated layered LiMnO2 was studied using hybrid eigenvector-following coupled with density functional theory. The initial part of the transformation mechanism of Li0.5MnO2 involves the migration of Li into both octahedral and tetrahedral local minima within the layered structure. The next stage of the transformation process involves the migration of Mn and was found to occur through several local minima, including an intermediate square pyramidal MnO5 configuration and an independent Mn3+ to Mn2+ charge-transfer process. The migration pathways were found to be significantly affected by the size of the supercell used and the inclusion of a Hubbard U parameter in the DFT functional. The transition state searching methodology described should be useful for studying the structural rearrangements that can occur in electrode materials during battery cycling, and more generally, ionic and electronic transport phenomena in a wide range of energy materials.",

author = "Seymour, {Ieuan D.} and Sudip Chakraborty and Middlemiss, {Derek S.} and Wales, {David J.} and Grey, {Clare P.}",

note = "Publisher Copyright: {\textcopyright} 2015 American Chemical Society. Acknowledgement: Via our membership of the U.K.'s HPC Materials Chemistry Consortium, which is funded by EPSRC (No. EP/L000202), this work made use of the facilities of HECToR and ARCHER, the U.K.'s national high-performance computing service, which is funded by the Office of Science and Technology through EPSRC's High End Computing Programme. Research was also carried out at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886. C.P.G acknowledges the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award #DE-SC0012583. I.D.S. would like to acknowledge funding from the Geoffrey Moorhouse Gibson Studentship in Chemistry from Trinity College Cambridge. S.C. would like to acknowledge Carl Tryggers Stiftelse for Vetenskaplig Forskning (CTS) and Rajeev Ahuja.",

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N2 - The migration mechanism associated with the initial layered-to-spinel transformation of partially delithiated layered LiMnO2 was studied using hybrid eigenvector-following coupled with density functional theory. The initial part of the transformation mechanism of Li0.5MnO2 involves the migration of Li into both octahedral and tetrahedral local minima within the layered structure. The next stage of the transformation process involves the migration of Mn and was found to occur through several local minima, including an intermediate square pyramidal MnO5 configuration and an independent Mn3+ to Mn2+ charge-transfer process. The migration pathways were found to be significantly affected by the size of the supercell used and the inclusion of a Hubbard U parameter in the DFT functional. The transition state searching methodology described should be useful for studying the structural rearrangements that can occur in electrode materials during battery cycling, and more generally, ionic and electronic transport phenomena in a wide range of energy materials.

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Mapping Structural Changes in Electrode Materials: Application of the Hybrid Eigenvector-Following Density Functional Theory (DFT) Method to Layered Li_0.5MnO₂

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